TWI733882B - Manufacturing method of laminated body and manufacturing method of electronic component - Google Patents

Abstract

The present invention provides a method for manufacturing a laminate with excellent adhesion and a method for manufacturing an electronic component. The manufacturing method includes: a photosensitive resin composition layer formation process, an exposure process, a development process, a heating process, and a metal layer formation process, between the photosensitive resin composition layer formation process and the exposure process, and the exposure process and the development process Perform a preservation process in at least one of between the development process and the heating process, and between the heating process and the metal layer forming process. In the preservation process, after the surface temperature reaches a certain temperature, it is stored in this state for more than 5 minutes .

Description

Manufacturing method of laminated body and manufacturing method of electronic component

The present invention relates to a method for manufacturing a laminate and a method for manufacturing an electronic component.

Resins such as polyimide and polybenzoxazole are excellent in heat resistance and insulating properties, so they are used in insulating layers of electronic components and the like. In addition, polyimine and polybenzoxazole have low solubility in solvents, so they are also applied in the state of precursors (polyimine precursors and polybenzoxazole precursors) before the cyclization reaction After the support, etc., it is heated to cyclize the polyimide precursor and the polybenzoxazole precursor to form a cured film.

For example, Patent Documents 1 and 2 describe the production of a patterned cured film using a photosensitive resin composition containing a polyimide precursor and a photopolymerization initiator. [Prior Technical Documents] [Patent Documents]

[Patent Document 1] Japanese Patent Application Publication No. 2011-191749 [Patent Document 2] Japanese Patent Application Publication No. 2014-201695

The present inventors conducted research on a photosensitive resin composition comprising a resin selected from the group consisting of polyimide precursor, polyimide, polybenzoxazole precursor and polybenzoxazole, and a photopolymerization initiator. As a result, it was found that a film formed using a photosensitive resin composition containing these resins sometimes has insufficient adhesion to a support or a metal layer.

The object of the present invention is to provide a method of manufacturing a laminate with excellent adhesiveness and a method of manufacturing an electronic component.

式（1）中，A²¹ 及A²² 分別獨立地表示氧原子或-NH-，R²¹ 表示2價有機基，R²² 表示4價有機基，R²³ 及R²⁴ 分別獨立地表示氫原子或1價有機基 ＜11＞如＜10＞所述之積層體的製造方法，其中 式（1）中，R²³ 及R²⁴ 中的至少一個包含自由基聚合性基。 ＜12＞如＜10＞或＜11＞所述之積層體的製造方法，其中 式（1）中的R²² 是包含芳香環之4價基團。 ＜13＞如＜1＞～＜12＞中任一項所述之積層體的製造方法，其中 將如下一系列的循環進行2循環以上，亦即於金屬層形成製程後的圖案上，依序進行感光性樹脂組成物層形成製程、曝光製程、顯影製程、加熱製程及金屬層形成製程，且將於感光性樹脂組成物層形成製程與曝光製程之間、曝光製程與顯影製程之間、顯影製程與加熱製程之間及加熱製程與金屬層形成製程之間中的至少一個中，進行保存製程 。 ＜14＞如＜1＞～＜13＞中任一項所述之積層體的製造方法，其為複數層配線結構的積層體的製造方法。 ＜15＞一種電子元件的製造方法，其包括： 感光性樹脂組成物層形成製程，於支撐體上應用包含選自聚醯亞胺前驅物、聚醯亞胺、聚苯并噁唑前驅物及聚苯并噁唑中之樹脂和光聚合起始劑之感光性樹脂組成物而形成感光性樹脂組成物層； 曝光製程，將感光性樹脂組成物層曝光成圖案狀； 顯影製程，對感光性樹脂組成物層進行顯影而形成圖案； 加熱製程，對圖案進行加熱；以及 金屬層形成製程，於加熱後的圖案上形成金屬層；並且 於感光性樹脂組成物層形成製程與曝光製程之間、曝光製程與顯影製程之間、顯影製程與加熱製程之間及加熱製程與金屬層形成製程之間中的至少一個中，進行保存製程，該保存製程中，於表面溫度達到一定溫度之後，於該狀態下保存5分鐘以上。 ＜16＞ 如＜15＞所述之電子元件的製造方法，其中 於相同的保存製程的條件下製造複數個電子元件。 [發明效果]Based on the above problems, the inventors have conducted research and found the following tendency to use resins selected from polyimide precursors, polyimines, polybenzoxazole precursors, and polybenzoxazoles After the film formed with the photosensitive resin composition of the photopolymerization initiator is applied to the support, it takes time to stabilize the properties of the film. Furthermore, it was found that by setting a predetermined preservation process in any one of the processes described below, it is possible to produce a laminate with excellent adhesion, and the above-mentioned problem is solved. The present invention provides the following. <1> A method for manufacturing a laminate, comprising: a process for forming a photosensitive resin composition layer, and applying on the support includes a precursor selected from the group consisting of polyimide, polyimide, polybenzoxazole, and The photosensitive resin composition of the resin in the polybenzoxazole and the photopolymerization initiator to form the photosensitive resin composition layer; the exposure process, the photosensitive resin composition layer is exposed into a pattern; the development process, the photosensitive resin The composition layer is developed to form a pattern; a heating process to heat the pattern; and a metal layer forming process to form a metal layer on the heated pattern; and between the photosensitive resin composition layer forming process and the exposure process, exposure Between the process and the development process, between the development process and the heating process, and between the heating process and the metal layer forming process, a preservation process is performed. In the preservation process, after the surface temperature reaches a certain temperature, the state is Keep it for more than 5 minutes. <2> The method for manufacturing a laminate as described in <1>, wherein the preservation process is performed between the exposure process and the development process. <3> The method of manufacturing a laminate as described in <2>, wherein the preservation process performed between the exposure process and the development process satisfies the following formula: 5≤t1<(10 ^{-0.036×T1+12.3} )×60 T1 It is the average surface temperature in the preservation process performed between the exposure process and the development process and the unit is K, and t1 is the time of the preservation process performed between the exposure process and the development process and the unit is minutes. <4> The method for producing a laminate according to any one of <1> to <3>, wherein a preservation process is performed between the photosensitive resin composition layer formation process and the exposure process. <5> The method for manufacturing a laminate as described in <4>, wherein the preservation process performed between the photosensitive resin composition layer formation process and the exposure process satisfies the following formula: 5≤t2<(10 ^{-0.031×T2 +10.7} )×60 T2 is the average surface temperature in the preservation process between the photosensitive resin composition layer formation process and the exposure process and the unit is K, t2 is the difference between the photosensitive resin composition layer formation process and the exposure process The time of the save process performed in the meantime and the unit is minutes. <6> The method for manufacturing a laminate according to any one of <1> to <5>, wherein a preservation process is performed between the development process and the heating process. <7> The method of manufacturing a laminate as described in <6>, wherein the storage process performed between the development process and the heating process satisfies the following formula: 5≤t3<(10 ^{-0.02×T3+8.0} )×60 T3 It is the average surface temperature in the preservation process performed between the development process and the heating process and the unit is K, and t3 is the time of the preservation process performed between the development process and the heating process and the unit is minutes. <8> The method for manufacturing a laminate according to any one of <1> to <7>, wherein a preservation process is performed between the heating process and the metal layer forming process. <9> The method for producing a laminate according to any one of <1> to <8>, wherein the resin in the photosensitive resin composition is a polyimide precursor, and the polyimide precursor contains free radicals The polymerizable group or the photosensitive resin composition contains a radical polymerizable compound other than the polyimide precursor. <10> The method for producing a laminate according to any one of <1> to <9>, wherein the polyimide precursor includes a repeating unit represented by the following formula (1). Formula (1) [Chemical Formula 1]

In formula (1), A ²¹ and A ²² each independently represent an oxygen atom or -NH-, R ²¹ represents a divalent organic group, R ²² represents a tetravalent organic group, and R ²³ and R ²⁴ each independently represent a hydrogen atom or Monovalent organic group <11> The method for producing a laminate as described in <10>, wherein in formula (1), ^{at least one of R 23} and R ²⁴ includes a radical polymerizable group. <12> The method for producing a laminate as described in <10> or <11>, wherein R ²² in the formula (1) is a tetravalent group containing an aromatic ring. <13> The method for manufacturing a laminate according to any one of <1> to <12>, wherein the following series of cycles are performed for 2 cycles or more, that is, on the pattern after the metal layer formation process, sequentially The photosensitive resin composition layer formation process, the exposure process, the development process, the heating process and the metal layer formation process are performed, and the photosensitive resin composition layer formation process and the exposure process, the exposure process and the development process, and the development process are performed. The preservation process is performed in at least one of between the manufacturing process and the heating process and between the heating process and the metal layer forming process. <14> The method of manufacturing a laminate according to any one of <1> to <13>, which is a method of manufacturing a laminate of a plural-layer wiring structure. <15> A method of manufacturing an electronic component, comprising: a process of forming a photosensitive resin composition layer, and applying it on a support comprising a precursor selected from the group consisting of polyimide, polyimide, polybenzoxazole, and The photosensitive resin composition of the resin in the polybenzoxazole and the photopolymerization initiator to form the photosensitive resin composition layer; the exposure process, the photosensitive resin composition layer is exposed into a pattern; the development process, the photosensitive resin The composition layer is developed to form a pattern; a heating process to heat the pattern; and a metal layer forming process to form a metal layer on the heated pattern; and between the photosensitive resin composition layer forming process and the exposure process, exposure Between the process and the development process, between the development process and the heating process, and between the heating process and the metal layer forming process, a preservation process is performed. In the preservation process, after the surface temperature reaches a certain temperature, the state is Keep it for more than 5 minutes. <16> The method of manufacturing electronic components as described in <15>, wherein a plurality of electronic components are manufactured under the same preservation process conditions. [Effects of the invention]

According to the present invention, it is possible to provide a method for manufacturing a laminate with excellent adhesion and a method for manufacturing an electronic component.

The description of the constituent elements of the present invention described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment. In the label of the group (atomic group) in this specification, the label that does not record substituted and unsubstituted means that both a group having no substituent and a group having a substituent are included. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl). As long as "exposure" in this specification is not particularly limited, in addition to exposure with light, drawing with particle beams such as electron beams and ion beams is also included in exposure. In addition, as the light used for exposure, there are usually actinic rays or radiations such as extreme ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, electron beams, etc. represented by the bright-ray spectrum of mercury lamps and excimer lasers. In this specification, the numerical range indicated by "～" refers to the range that includes the numerical values described before and after "～" as the lower limit and the upper limit. In this manual, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)allyl" means "allyl" and "methacrylate". "(Meth)acrylic acid" means both or either of "acrylic acid" and "methacrylic acid", "(meth)acrylic acid" means "acrylic acid" Either or either of the "base" and "methacryloyl". In this manual, the term "process" is not only an independent process, but even if it cannot be clearly distinguished from other processes, if the intended effect of the process can be achieved, it is also included in this term. In this specification, the solid content concentration refers to the mass percentage of components other than the solvent relative to the total mass of the composition. In addition, unless otherwise stated, the solid content concentration means the concentration at 25°C. In this specification, unless otherwise stated, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured based on gel permeation chromatography (GPC), and are defined as styrene conversion values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super can be used as the columns. HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). As long as there is no special description, the eluent will be measured with THF (tetrahydrofuran). In addition, as long as there is no special description, the detection is made to use a UV ray (ultraviolet) wavelength 254 nm detector.

<The manufacturing method of the laminated body> The manufacturing method of the laminated body of the present invention is characterized by comprising: a photosensitive resin composition layer forming process, and applying a layer selected from the group consisting of polyimide precursors, polyimides, and The photosensitive resin composition of the polybenzoxazole precursor and the resin in the polybenzoxazole and the photopolymerization initiator to form the photosensitive resin composition layer; the exposure process, the photosensitive resin composition layer is exposed into a pattern ; Development process, the photosensitive resin composition layer is developed to form a pattern; heating process, the pattern is heated; and the metal layer forming process, the metal layer is formed on the heated pattern, and the photosensitive resin composition layer is formed Between the exposure process, between the exposure process and the development process, between the development process and the heating process, and between the heating process and the metal layer forming process, the preservation process is performed. The preservation process is performed at the surface temperature After reaching a certain temperature, store in this state for more than 5 minutes.

According to the present invention, a laminate with excellent adhesion can be formed. The reason for obtaining such an effect is presumed to be based on the following. The film formed using the photosensitive resin composition containing the said resin and a photopolymerization initiator has a tendency to take time until the properties of the film become stable. It is believed that if the next process is performed in a state where the properties of the film are not stable (for example, after the photosensitive resin composition layer formation process, followed by the exposure process, etc.), there will be localized reaction sites in the film Etc., thereby applying local stress to the film. In contrast, it is considered that according to the present invention, the provision of the storage process during any period of the various processes described above can stabilize the properties of the film and perform the next process in a state where the residual stress and the like of the film are alleviated. Therefore, it is estimated that a laminate with excellent adhesiveness can be produced. In addition, the above-mentioned resin in the photosensitive resin composition is a polyimide precursor, and the polyimine precursor contains a radical polymerizable group or contains a radical polymerizable group other than the polyimine precursor. In the case of a photosensitive resin composition of a compound, the effect of the present invention is particularly remarkable. Although the detailed reason is not clear, it uses a photosensitive compound containing this kind of radical polymerizable component (a polyimide precursor with a radical polymerizable group, a radical polymerizable compound other than the polyimide precursor) In the case of flexible resins, during the exposure process and the development process, the crosslinking reaction based on the radical polymerization of the radical polymerizable component is used to form the pattern, and the resulting pattern is heated at a high temperature during the heating process to initiate the imine Chemical reaction to form a highly heat-resistant, highly insulating film. In this way, in the case of using a photosensitive composition containing the above-mentioned radically polymerizable components, the reaction is complicated in multiple stages, but it is presumed that by setting the above-mentioned preservation process, the microstate of the film can be stabilized and the formed film can be stabilized. The properties of the film are stable and a laminate with excellent adhesion is produced. Hereinafter, each process in the manufacturing method of the laminated body of this invention is demonstrated.

(Photosensitive resin composition layer formation process) The manufacturing method of the laminate of the present invention includes a photosensitive resin composition layer formation process of applying a photosensitive resin composition to a support to form a photosensitive resin composition layer. The photosensitive resin composition will be described later.

The type of support can be appropriately determined according to the application. For example, an inorganic substrate, a resin substrate, a resin composite substrate, etc. can be cited. Examples of inorganic substrates include glass substrates, quartz substrates, silicon substrates, silicon nitride substrates, and composite substrates in which molybdenum, titanium, aluminum, copper, etc. are vapor-deposited on such substrates. Examples of resin substrates include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, and polycarbonate. Ester, polyether, polyether, polyarylate, allyl diethylene glycol carbonate, polyamide, polyimide, polyimide imine, polyether imine, polybenzazole, poly Phenyl sulfide, polycyclic olefin, norbornene resin, polychlorotrifluoroethylene and other fluororesins, liquid crystal polymers, acrylic resins, epoxy resins, silicone resins, ionomer resins, cyanate ester resins, cross-linked resins Substrates made of synthetic resins such as diesters of butenedioic acid, cyclic polyolefins, aromatic ethers, maleimides, olefins, cellulose, and episulfide compounds. These substrates are rarely used directly in the above-mentioned form. Usually, depending on the form of the final product, for example, a multiple-layered structure like a thin film transistor (TFT) element is formed. In addition, when the surface of the photosensitive resin composition layer or the surface of the metal layer further forms the photosensitive resin composition layer, the photosensitive resin composition layer or the metal layer serves as a support.

As a method of applying the photosensitive resin composition to the support, coating is preferred. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, and slit scanning. Method, inkjet method, etc. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, the spin coating method is more preferable. In the case of a spin coating method, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute. Regarding the thickness of the photosensitive resin composition layer, it is preferable to apply it so that the film thickness after exposure becomes 0.1-100 micrometers, and it is more preferable to apply it so that it may become 1-50 micrometers. In addition, the thickness of the photosensitive resin composition layer formed is not necessarily uniform. For example, when a photosensitive resin composition layer is formed on a surface having unevenness, it may become a photosensitive resin composition layer with different thicknesses.

In the process of forming the photosensitive resin composition layer, the photosensitive resin composition layer formed on the support may be dried. The drying temperature is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. The drying time is preferably 30 seconds to 20 minutes, more preferably 1 to 10 minutes, and even more preferably 3 to 7 minutes. In addition, the drying process is a process different from the preservation process in the present invention.

(Exposure process) In the manufacturing method of the laminated body of this invention, the exposure process which exposes the said photosensitive resin composition layer in pattern form is included. The exposure is not particularly limited as long as the photosensitive resin composition can be cured. For example, the exposure energy at a wavelength of 365 nm ^{is preferably 100 to 10000 mJ/cm 2,} and it is more preferably 200 to 8000 mJ/cm ² . The exposure wavelength can be appropriately set in the range of 190 to 1000 nm, preferably 240 to 550 nm.

(Development process) The manufacturing method of the laminate of the present invention includes a development process of developing the photosensitive resin composition layer to form a pattern with respect to the photosensitive resin composition layer that has been exposed. The development is performed using a developer. The developer can be used without particular limitation. Solvents are preferred. Examples of the solvent used in the developer include organic solvents such as esters, ethers, ketones, aromatic hydrocarbons, and sulfites. About these details, the solvent demonstrated in the column of the resin composition mentioned later can be mentioned. Among them, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3- Methyl methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate , Propylene glycol methyl ether and propylene glycol methyl ether acetate are preferred, and cyclopentanone and γ-butyrolactone are more preferred.

As the development time, 10 seconds to 5 minutes are preferred. The temperature during development is not particularly limited, and it can be performed at 20 to 40°C. After the treatment with the developer, it can be further rinsed. It is better to use a solvent different from that of the developer during the rinsing process. For example, the solvent contained in the photosensitive resin composition can be used for rinsing. The rinse time is preferably 5 seconds to 1 minute.

(Heating process) The manufacturing method of the laminated body of the present invention includes a heating process of heating the pattern (resin layer) obtained by the development process. In the heating process, the cyclization reaction of the polyimide precursor and the like is carried out. In addition, curing of unreacted radical polymerizable components and the like are also performed. As the maximum heating temperature (the maximum temperature during heating), 100 to 500°C is preferable, 140 to 400°C is more preferable, and 160 to 350°C is still more preferable. Regarding heating, it is preferable to perform heating from a temperature of 20 to 150°C to the maximum heating temperature at a temperature increase rate of 1 to 12°C/min, more preferably 2 to 10°C/min, and still more preferably 3 to 10°C/min. By setting the heating rate to 2°C/min or more, it is possible to ensure high productivity while preventing the amine from being too volatilized, and by setting the heating rate to 12°C/min or less, the residual stress in the resulting film can be relaxed . The temperature at the start of heating is preferably 20 to 150°C, more preferably 20 to 130°C, and even more preferably 25 to 120°C. The temperature at the start of heating refers to the heating temperature when the process of heating to the highest heating temperature is started. For example, when the photosensitive resin composition is applied to a substrate and dried, the temperature after drying is used, for example, gradually from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the photosensitive resin composition It is better to increase the temperature. Regarding heating, after reaching the maximum heating temperature, heating is preferably performed for 10 to 360 minutes, heating is more preferably performed for 20 to 300 minutes, and heating is particularly preferably performed for 30 to 240 minutes.

Heating can be carried out in stages. As an example, there can be a process of raising temperature from 25°C to 180°C at 3°C/min, leaving it at 180°C for 60 minutes, and heating it from 180°C to 200°C at 2°C/min, and leaving it at 200°C for 120 minutes. . Furthermore, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5°C/min.

Regarding the heating process, from the viewpoint of preventing the decomposition of the polyimide precursor, it is better to perform it in an environment of low oxygen concentration by flowing inert gas such as nitrogen, helium, and argon. The oxygen concentration is preferably 50 volume ppm or less, and more preferably 20 volume ppm or less.

(Metal layer forming process) The manufacturing method of the laminate of the present invention includes a metal layer forming process of forming a metal layer on the pattern (resin layer) after heating. The metal layer is not particularly limited, and known metal types can be used. For example, copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten can be cited. Copper and aluminum are preferred, and copper is more preferred. The method of forming the metal layer is not particularly limited, and a known method can be used. For example, the methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, and Japanese Patent Application Publication No. 2004-101850 can be used. For example, photolithography, peeling, electroplating, electroless plating, etching, printing, and methods combining them can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography with electrolytic plating can be cited. As for the thickness of the metal layer, the thickest part is preferably 0.1-50 μm, more preferably 1-10 μm.

(Surface activation treatment process) The manufacturing method of the laminate of the present invention may include a surface activation treatment process of subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment. The surface activation treatment may be performed only on at least a part of the metal layer. It may be performed on at least a part of the photosensitive resin composition layer after the heating process, or may be performed on at least a part of both the metal layer and the photosensitive resin composition layer after the heating process. The surface activation treatment process usually enters after the metal layer formation process, but after the above heating process, the photosensitive resin composition layer may be subjected to a surface activation treatment process to form the metal layer. It is preferable to perform the surface activation treatment on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on all parts of the area where the photosensitive resin composition layer is formed on the surface of the metal layer. In this way, by performing surface activation treatment on the surface of the metal layer, the adhesion with the photosensitive resin composition layer provided on the surface can be improved. In addition, the surface activation treatment may preferably be performed on part or all of the photosensitive resin composition layer after the heating process. In this way, by subjecting the surface of the photosensitive resin composition layer to surface activation treatment, it is possible to improve the adhesion to the metal layer or photosensitive resin composition layer provided on the surface that has been subjected to the surface activation treatment. The surface activation treatment is selected from various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.) plasma treatment, corona discharge treatment, based on CF ₄ /O ₂ , Etching treatment of NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ , surface treatment based on ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film The impregnation treatment with the organic surface treatment agent of at least one compound in the base, the mechanical roughening treatment using a brush, the plasma treatment is preferred, and the oxygen plasma treatment using oxygen is particularly preferred for the raw material gas. When corona discharge treatment is performed, the energy is ^{preferably 500 to 200,000 J/m 2} , more preferably 1,000 to 100,000 J/m ² , and 10,000 to 50,000 J/m ² is the best.

(Preservation process) In the manufacturing method of the laminate of the present invention, between the photosensitive resin composition layer formation process and the exposure process, between the exposure process and the development process, between the development process and the heating process, and between the heating process and the metal layer formation In any one of the processes, a preservation process is performed in which the surface temperature reaches a certain temperature and is stored in this state for more than 5 minutes. The above-mentioned preservation process can be carried out between all existing processes, or can be carried out only in any one of the processes, or the above-mentioned preservation process can also be carried out. In the present invention, it is preferable to perform the preservation process in at least one of the photosensitive resin composition layer formation process and the exposure process, between the exposure process and the development process, and between the development process and the heating process. The preservation process between the development process is better. The preservation process between the exposure process and the development process can further improve the adhesiveness of the photosensitive resin composition layer.

In the present invention, the preservation process refers to a process in which the surface temperature reaches a certain temperature and is stored in this state for more than 5 minutes. Here, the surface temperature refers to the surface temperature of the processed object such as a pattern (resin layer) formed by the photosensitive resin composition layer or the photosensitive resin composition layer.

In the present invention, a certain temperature in the storage process does not refer to a certain temperature, but can have a specified temperature range. The range of variation (the difference between the maximum value and the minimum value of the surface temperature) of the surface temperature of the processed object during the storage process is preferably 15°C or less, more preferably 10°C or less, and even more preferably 5°C or less. If the fluctuation range of the surface temperature is in the above range, the properties of the film can be stabilized, and a laminate with excellent adhesiveness can be easily produced.

In the present invention, the average surface temperature of the processed object in the storage process is preferably -30°C or higher, more preferably 4°C or higher, more preferably 10°C or higher, and particularly preferably 20°C or higher. The upper limit is preferably 100°C or lower, more preferably 60°C or lower, more preferably 45°C or lower, and particularly preferably 30°C or lower. In addition, the average surface temperature of the object to be processed means the average of the surface temperature of the object to be processed per hour. In addition, the preservation process is carried out for more than 5 minutes.

When the preservation process is performed between the exposure process and the development process (hereinafter, the preservation process will also be referred to as a PED (Post Exposure Delay) process), the PED process is better performed under the condition that the following formula is satisfied. 5≤t1<(10 ^{-0.036×T1+12.3} )×60 T1 is the average surface temperature in the PED process and the unit is K, and t1 is the time of the PED process and the unit is minutes.

In addition, the average surface temperature of the object to be processed in the PED process is preferably -30 to 60°C, more preferably 4 to 45°C, and even more preferably 20 to 30°C. In addition, the PED process is preferably performed for 5 to 720 minutes, more preferably for 5 to 480 minutes, and even more preferably for 5 to 360 minutes. The variation range of the surface temperature of the processed object in the PED process is preferably 15°C or less, more preferably 10°C or less, and even more preferably 5°C or less.

When the preservation process is performed between the photosensitive resin composition layer formation process and the exposure process (hereinafter, the preservation process is also referred to as PCD (Post Coating Delay) process), the PCD process satisfies the following formula It is better to proceed under the conditions. 5≤t2<(10 ^{-0.031×T2+10.7} )×60 T2 is the average surface temperature in the PCD process and the unit is K, and t2 is the time of the PCD process and the unit is minutes.

In addition, the average surface temperature of the processed object in the PCD process is preferably -30 to 60°C, more preferably 4 to 45°C, and even more preferably 20 to 30°C. In addition, the PCD process is preferably only 5 to 360 minutes, more preferably 5 to 120 minutes, and even more preferably 5 to 60 minutes. The variation range of the surface temperature of the processed object in the PCD process is preferably 15°C or less, more preferably 10°C or less, and even more preferably 5°C or less.

When the preservation process is performed between the development process and the heating process (hereinafter, the preservation process is also referred to as a PDD (Post Developing Delay) process), the PDD process is preferably performed under the condition that the following formula is satisfied. 5≤t3<(10 ^{-0.02×T3+8.0} )×60 T3 is the average surface temperature in the PDD process and the unit is K, and t3 is the time of the PDD process and the unit is minutes.

In addition, the average surface temperature of the processed object in the PDD process is preferably 4 to 80°C, more preferably 10 to 60°C, and even more preferably 20 to 30°C. In addition, the PDD process is preferably performed for 5 to 1200 minutes, more preferably for 5 to 720 minutes, more preferably for 5 to 600 minutes, and particularly preferably for 5 to 300 minutes. The variation range of the surface temperature of the processed object in the PDD process is preferably 30°C or less, more preferably 20°C or less, and even more preferably 10°C or less.

When the preservation process is performed between the heating process and the metal layer formation process (hereinafter, the preservation process will also be referred to as PBD (Post Bake Delay) process), the average surface temperature of the processed object in the PBD process is 4 to 100°C is preferred, 10 to 80°C is more preferred, and 20 to 60°C is even more preferred. In addition, the PBD process is preferably carried out for 5 to 2400 minutes, more preferably for 5 to 1200 minutes, more preferably for 5 to 900 minutes, and particularly preferably for 5 to 600 minutes. The variation range of the surface temperature of the object to be processed in the PBD process is preferably 60°C or less, more preferably 45°C or less, and more preferably 30°C or less.

The manufacturing method of the laminated body of the present invention preferably performs the following series of cycles for 2 cycles or more, that is, the photosensitive resin composition layer is formed sequentially on the pattern (resin layer) after the metal layer formation process Process, exposure process, development process, heating process and metal layer formation process, and between photosensitive resin composition layer formation process and exposure process, exposure process and development process, development process and heating process, and heating process The preservation process is performed in at least any one of the metal layer forming processes. The aforementioned cycle is preferably performed 2 to 7 times, and more preferably 2 to 5 times. Thereby, it is possible to manufacture a laminated body of a plural-layer wiring structure in which a resin layer formed of a photosensitive resin composition layer and a metal layer are alternately laminated in plural layers. In addition, as the number of layers increases, peeling is likely to occur at the interface between the metal layer and the resin layer, the interface between the resin layers, and the interface between the resin layer and the support. The number will not produce peeling between the layers. Therefore, the effect of the present invention can be obtained more remarkably.

Fig. 1 is a diagram showing an example of a laminate having a wiring structure of plural layers. In the figure, reference numeral 500 represents a laminate, reference numerals 201 to 204 represent resin layers, and reference numerals 301 to 303 represent metal layers. A desired pattern is formed in the resin layer 201. For example, the pattern can be formed by negative-tone development, for example. A metal layer 301 is formed on the surface of the resin layer 201. The metal layer 301 is formed to cover a part of the surface of the groove 401 formed in the resin layer 201. A resin layer 202 is formed on the metal layer 301. A desired pattern is formed in the resin layer 202 and a part of the metal layer 301 is exposed on the resin layer 202. A metal layer 302 is formed on the surface of the resin layer 202. The metal layer 302 is formed to cover a part of the surface of the groove 402 formed in the resin layer 202 and is electrically connected to the metal layer 301 exposed on the resin layer 202. A resin layer 203 is formed on the metal layer 302. A desired pattern is formed in the resin layer 203, and a part of the metal layer 302 is exposed on the resin layer 203. A metal layer 303 is formed on the surface of the resin layer 203. The metal layer 303 is formed to cover a part of the surface of the groove 403 formed in the resin layer 203 and is electrically connected to the metal layer 302 exposed on the resin layer 203. A resin layer 204 is formed on the metal layer 303. A desired pattern is formed in the resin layer 204, and a part of the metal layer 303 is exposed on the resin layer 204. Moreover, a part of the metal layer 302 in FIG. 1 is also exposed on the resin layer 204. The laminate functions as an insulating film of the resin layers 201 to 204, and the metal layers 301 to 303 function as wiring layers. This type of laminate can be preferably used as a rewiring layer in electronic components.

<Photosensitive resin composition (resin composition)> Next, the photosensitive resin composition (hereinafter, also referred to as a resin composition) used in the method for producing a laminate of the present invention will be described.

<<Resin>> The resin composition in the present invention includes a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. When a polyimide precursor or a polybenzoxazole precursor is used as the resin, it tends to be difficult to stabilize the film properties. Therefore, when a polyimide precursor or a polybenzoxazole precursor is used as the resin, the effects of the present invention can be particularly remarkably obtained. Among them, when a polyimide precursor (preferably, a polyimide precursor having a radical polymerizable group) is used as the resin, the effects of the present invention can be particularly remarkably obtained.

The content of the resin in the resin composition relative to the total solid content of the resin composition is preferably 20 to 99% by mass, more preferably 50 to 99% by mass, more preferably 60 to 99% by mass, and 70 to 99% by mass % Is particularly good. In addition, the content of the resin in the resin composition is preferably 20 to 99% by mass relative to the total solid content of the resin composition, more preferably 50 to 99% by mass, more preferably 60 to 99% by mass, and 70 to 99% by mass is particularly good. In addition, the content of the polyimide precursor in the total mass of the resin contained in the resin composition is preferably 80-100% by mass, more preferably 90-100% by mass. It is preferable that the resin contained in the resin composition consists essentially of polyimide only. The fact that the resin contained in the resin composition consists essentially only of polyimide means that, for example, the content of the resin other than the polyimine precursor contained in the resin is the content of the polyimide precursor 3% by mass or less is preferable.

式（1）中，A²¹ 及A²² 分別獨立地表示氧原子或-NH-，R²¹ 表示2價有機基，R²² 表示4價有機基，R²³ 及R²⁴ 分別獨立地表示氫原子或1價有機基。(Polyimine precursor) As the polyimine precursor, a polyimine precursor containing a repeating unit represented by formula (1) is preferred. Formula (1) [Chemical Formula 2]

In formula (1), A ²¹ and A ²² each independently represent an oxygen atom or -NH-, R ²¹ represents a divalent organic group, R ²² represents a tetravalent organic group, and R ²³ and R ²⁴ each independently represent a hydrogen atom or Monovalent organic group.

A ²¹ and A ²² each independently represent an oxygen atom or -NH-, and an oxygen atom is preferred.

R ²¹ represents a divalent organic group. Examples of divalent organic groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aryl groups, straight-chain or branched aliphatic groups with 2 to 20 carbons, and cyclic groups with 6 to 20 carbons. An aliphatic group, an aryl group having 6 to 20 carbons, or a group including a combination thereof is preferable, and a group including an aryl group having 6 to 20 carbons is more preferable. As an example of an aryl group, the following can be mentioned.

式中，A是單鍵或選自可以被氟原子取代之碳數1～10的烴基、-O-、-C（=O）-、-S-、-S（=O）₂ -及-NHCO-、以及它們的組合中之基團為較佳，單鍵或選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-、-SO₂ -中之基團為更佳，選自-CH₂ -、-O-、-S-、-SO₂ -、-C（CF₃ ）₂ -、-C（CH₃ ）₂ -中之2價基為進一步較佳。[Chemical formula 3]

In the formula, A is a single bond or is selected from a hydrocarbon group with 1 to 10 carbons which can be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -and- Groups in NHCO- and their combinations are preferred, single bonds or selected from alkylene groups with 1 to 3 carbons which may be substituted by fluorine atoms, -O-, -C(=O)-, -S The group in -, -SO ₂ -is more preferably selected from -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ The divalent group in-is further preferred.

Specifically, R ²¹ includes the diamine residue remaining after removal of the amine group of the following diamine, and the like. Selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diamine Cyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, Bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone two Amine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminodiphenyl and 3,3'-diaminodiphenyl, 4,4'-diaminodiphenyl ether And 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide Benzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4' -Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4 -Aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) Phenyl) chrysene, bis(4-amino-3-hydroxyphenyl) chrysene, 4,4'-diamino p-terphenyl, 4,4'-bis(4-aminophenoxy) biphenyl, Bis[4-(4-aminophenoxy)phenyl] chrysene, bis[4-(3-aminophenoxy) phenyl] chrysene, bis[4-(2-aminophenoxy) benzene Yl] benzene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-bis Amino diphenyl benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene Group) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4, 4'-Diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4 '-Tetraamino diphenyl ether, 1,4-diamino anthraquinone, 1,5-diamino anthraquinone, 3,3-dihydroxy-4,4'-diamino biphenyl, 9,9 '-Bis(4-aminophenyl) 茀、4,4'-bis Methyl-3,3'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminodiphenylmethane Cumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2, 4,6-Trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1, 2-bis(4-aminophenyl)ethane, diaminobenzaniline, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3- Bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1 ,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4- (2-Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2, 2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy) Benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy) ) Biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfide, 4,4'-bis(3-amino-5-trifluoromethylbenzene Oxy) diphenyl sulfide, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetra Methyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis At least one diamine among (trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotoluidine, and 4,4'-diaminotetrabiphenyl.

In addition, as ^{an example of R 21} , the diamine residues remaining after removal of the amine group of the diamines (DA-1) to (DA-18) shown below can also be cited.

[Chemical formula 4]

[Chemical formula 5]

Moreover, as ^{an example of R 21} , the diamine residue remaining after removal of the amine group of the diamine having two or more alkylene glycol units in the main chain can also be cited. It is preferable to combine diamine residues containing two or more of ethylene glycol chains and propylene glycol chains or both in one molecule, and it is more preferable to combine diamine residues that do not contain aromatic rings. As an example, JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 ( The above are trade names, manufactured by HUNTSMAN Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-( 2-Aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., but it is not limited thereto. The structures of JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.

[Chemical formula 6]

In the above, x, y, and z are average values.

In the formula (1), R ²² represents a tetravalent organic group, and a tetravalent group containing an aromatic ring is preferred, and a group represented by the following formula (1-1) or formula (1-2) is more preferred.

式（1-1）中，R¹¹² 是單鍵或選自可以被氟原子取代之碳數1～10的烴基、-O-、-CO-、-S-、-SO₂ -及-NHCO-、以及它們的組合中之基團為較佳，單鍵或選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-CO-、-S-及-SO₂ -中之2價基團為更佳，選自包括-CH₂ -、-C（CF₃ ）₂ -、-C（CH₃ ）₂ -、-O-、-CO-、-S-及-SO₂ -之組中之2價基團為進一步較佳。Formula (1-1) [Chemical Formula 7]

In the formula (1-1), R ¹¹² is a single bond or is selected from a hydrocarbon group with 1 to 10 carbons which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -and -NHCO- , And the groups in their combinations are preferred, single bonds or selected from alkylene groups with 1 to 3 carbons which may be substituted by fluorine atoms, -O-, -CO-, -S- and -SO _2- Among them, the divalent group is more preferable, and is selected from -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO _The divalent group in the 2-group is more preferable.

Formula (1-2) [Chemical Formula 8]

Regarding R ²² , the tetracarboxylic acid residue remaining after removing the acid anhydride group from the tetracarboxylic dianhydride, etc. may be mentioned. Specifically, the tetracarboxylic acid residue etc. which remain after removing an acid anhydride group from the following tetracarboxylic dianhydride are mentioned. Selected from pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'- Diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2, 3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1, 4,5,7-Naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride , 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4 ,5,6-Naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2, 4,5-Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride, 1,1-bis(2,3 -Dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride and their carbon numbers At least one tetracarboxylic dianhydride among alkyl derivatives of 1 to 6 and alkoxy derivatives of 1 to 6 carbon atoms.

In addition, ^{examples of R 22} include tetracarboxylic acid residues remaining after removing acid anhydride groups from tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below. [Chemical formula 9]

From the viewpoint of solubility with respect to an alkali developer, it ^{is preferable that R 22} has an OH group. More specifically, as R ²² , a tetracarboxylic acid residue remaining after removing an acid anhydride group from the above-mentioned (DAA-1) to (DAA-5) can be mentioned.

In formula (1), R ²³ and R ²⁴ each independently represent a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group represented by R ²³ and R ²⁴ include a group containing a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, a radical polymerizable group, and the like. In the present invention, ^{at least one of R 23} and R ²⁴ includes a radical polymerizable group. According to this aspect, there is a tendency to obtain the effects of the present invention more remarkably. Moreover, the photosensitive resin composition containing this polyimide precursor can be used suitably as a negative photosensitive resin composition. As a radical polymerizable group, the group etc. which have an ethylenically unsaturated bond are mentioned. As a specific example of a radical polymerizable group, a vinyl group, a (meth)allyl group, the group represented by following formula (III), etc. are mentioned.

[Chemical formula 10]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferred. In the formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -or a polyoxyalkylene group having 4 to 30 carbon atoms. Examples of preferred R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene Methylene, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, ethylene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ -are more good. The combination of R ²⁰⁰ being a methyl group and R ²⁰¹ being an ethylene group is particularly preferred.

The carbon number of the straight-chain or branched alkyl group is preferably 1-30. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, Isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and camphenyl Group, dicyclohexyl and pinenyl (pinenyl). Among them, from the viewpoint of achieving high sensitivity, cyclohexyl is preferred. Examples of the aromatic group include substituted or unsubstituted benzene ring group, naphthyl ring group, pentenyl ring group, indenyl ring group, azulene ring group, heptene ring group, indenene ring group, and perylene ring group. , Fused pentaphenyl ring group, acenaphthylene ring group, phenanthrene ring group, anthracenyl ring group, fused tetraphenyl ring group, triphenyl ring group, terphenylene ring group, stilbene ring group, biphenyl ring group, pyrrole ring group, furan Cyclic, thiophene, imidazole, oxazole, thiazolyl, pyridine, pyrazine, pyrimidine, pyridazine, indolazine, indole, benzene O-furan ring group, benzothiophene ring group, isobenzofuran ring group, quinazine ring group, quinoline ring group, phthalazine ring group, naphthyridin ring group, quinoxaline ring group, quinoxazoline ring group , Isoquinoline ring group, carbazole ring group, phenanthridinyl ring group, acridine ring group, phenanthroline ring group, thioanthrane ring group, chromene ring group, xanthene ring group, phenanthrene ring group, phenanthrene ring group Phenazine ring group or phenazine ring group. A phenyl ring group is preferred.

In formula (1), when A ²² is an oxygen atom and R ²³ is a hydrogen atom and/or A ²¹ is an oxygen atom and R ²⁴ is a hydrogen atom, the polyimide precursor may be combined with an ethylenically unsaturated bond The tertiary amine compound forms a conjugate base. Examples of tertiary amine compounds having such ethylenically unsaturated bonds include N,N-dimethylaminopropyl methacrylate.

In addition, in the case of alkali development, it is preferable that the polyimide precursor has a fluorine atom in the structural unit from the viewpoint of improving the resolution. With fluorine atoms, it is possible to impart water repellency to the film surface at the time of alkali development, and to suppress penetration from the surface. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and from the viewpoint of solubility in an alkaline aqueous solution, 20% by mass or less is more preferable.

In addition, for the purpose of improving the adhesion to the substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

Furthermore, in order to improve the storage stability of the resin composition, it is preferable to seal the main chain end of the polyimide precursor with a blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monochloride compound, monoactive ester compound, and the like. Among these, it is more preferable to use monoamine. Preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-amino Naphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene Naphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid , 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6- Dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, or a plurality of different terminal groups may be introduced by reacting a plurality of capping agents.

The polyimide precursor may be composed of the repeating unit represented by formula (1) and other repeating units as other polyimine precursors. When other repeating units are included, the proportion of other repeating units in the polyimide precursor is preferably 1-60 mol%, more preferably 5-50 mol%.

The polyimide precursor in the present invention can also be constituted so as not to substantially contain other polyimide precursors other than the polyimide precursor containing the repeating unit represented by formula (1). Substantially not contained means that, for example, the content of the other polyimide precursor contained in the resin composition is 3% by mass or less of the content of the polyimide precursor.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 20,000-28,000, more preferably 22,000-27,000, and still more preferably 23,000-25,000. The degree of dispersion (Mw/Mn) of the polyimide precursor is not particularly determined, but 1.0 or more is preferable, 2.5 or more is more preferable, and 2.8 or more is even more preferable. The upper limit of the degree of dispersion of the polyimide precursor is not particularly limited. For example, 4.5 or less is preferable, and it can also be 3.4 or less.

式（4）中，R¹³¹ 表示2價有機基，R¹³² 表示4價有機基。(Polyimine) The polyimide used in the present invention may be a polymer compound having an imine ring, and it is not particularly limited, but a compound represented by the following formula (4) is preferred. A compound represented by the following formula (4), and a compound having a radical polymerizable group is more preferable. As the radical polymerizable group, the polymerizable group described with the polyimide precursor mentioned above can be mentioned, and the preferable range is also the same. Formula (4) [Chemical Formula 11]

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.

式中，R¹³³ 為自由基聚合性基，其他基團的定義與式（4）相同。 式（4-2） [化學式13]

式中，R¹³⁴ 及R¹³⁵ 中的至少一個是自由基聚合性基，另一個是有機基，其他基團的定義與式（4）相同。When the polyimide has a radical polymerizable group, a radical polymerizable group may be ^{introduced into at least one of R 131} and R ¹³² , as shown in the following formula (4-1) or formula (4-2) , A radical polymerizable group may be introduced at the end of the polyimide. Formula (4-1) [Chemical Formula 12]

In the formula, R ¹³³ is a radical polymerizable group, and the definitions of other groups are the same as those in the formula (4). Formula (4-2) [Chemical formula 13]

In the formula, ^{at least one of R 134} and R ¹³⁵ is a radical polymerizable group, the other is an organic group, and the definition of the other groups is the same as that of the formula (4).

As the divalent organic group represented by R ^{131 , the same group as R 21} in the formula (1) of the polyimide precursor described above can be exemplified, and the preferred range is also the same. As the tetravalent organic group represented by R ^{132 , the same group as R 22} in the formula (1) of the polyimide precursor described above can be exemplified, and the preferred range is also the same.

The imidization rate of polyimide is preferably 85% or more, and more preferably 90% or more. The imidization rate is 85% or more, whereby the shrinkage of the closed-loop film caused when the imidization is caused by heating is reduced, and the occurrence of warpage can be suppressed.

The polyimide not only contains the repeating structural unit of the above formula (4), which is based on one type of R ¹³¹ or R ¹³² , but also may contain two or more repeating units ^{of R 131} or R ^{132 of different types.} Moreover, in addition to the repeating unit of the above-mentioned formula (4), the polyimide may also include other types of repeating structural units.

Polyimine can be synthesized, for example, by the following method, which is a method of reacting a tetracarboxylic dianhydride with a diamine compound (used as a monoamine capping agent to replace a part) at a low temperature, and at a low temperature A method of reacting tetracarboxylic dianhydride (used as an acid anhydride or monoacid chloride compound or monoactive ester compound as a part of the blocking agent) with a diamine compound, obtained by tetracarboxylic dianhydride and alcohol The diester is then reacted with a diamine (used as a monoamine capping agent to replace part) in the presence of a condensing agent. The diester is obtained by tetracarboxylic dianhydride and alcohol, and then the remaining diamine The polyimide precursor is obtained by the method of chlorinating the carboxylic acid to react with the diamine (used as a monoamine capping agent to replace part) and other methods, and then complete it by the known imidization reaction method. The method of imidization or the method of stopping the imidation reaction halfway and introducing an imidine structure locally, and then mixing the fully imidized polymer and the polyimide precursor to locally introduce the imidation Method of imine structure. As a commercially available product of polyimide, Durimide (registered trademark) 284 (manufactured by Fujifilm Corporation) and Matrimide 5218 (manufactured by HUNTSMAN CORPORATION) can be exemplified.

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain a cured film with excellent mechanical properties, the weight average molecular weight is more preferably 20,000 or more. In addition, when two or more types of polyimines are contained, the weight average molecular weight of at least one type of polyimines is preferably within the above-mentioned range.

式（3）中，R¹²¹ 表示2價有機基，R¹²² 表示4價有機基，R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價有機基。(Polybenzoxazole precursor) In the present invention, as the polybenzoxazole precursor, the structure and the like are not particularly limited, but a compound containing a repeating unit represented by the following formula (3) is preferred. Formula (3) [Chemical Formula 14]

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

In formula (3), ^{the definitions of R 123} and R ^{124 are the same as those of R 23} in formula (1), and the preferred ranges are also the same.

In formula (3), as ^{the divalent organic group represented by R 121,} it is preferable to include at least one of an aliphatic group and an aromatic group. As the aliphatic group, a straight-chain aliphatic group is preferred. R ¹²¹ is preferably a dicarboxylic acid residue. As the dicarboxylic acid, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid containing an aromatic group are preferable, and a dicarboxylic acid containing an aromatic group is more preferable. As dicarboxylic acids containing aliphatic groups, dicarboxylic acids containing linear or branched (preferably linear) aliphatic groups are preferred. A dicarboxylic acid composed of two COOH is more preferable. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2-30, more preferably 2-25, more preferably 3-20, particularly preferably 4-15, and 5-10 To be further preferred. The straight-chain aliphatic group is preferably an alkylene group. Specific examples of dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid Acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid , Adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluoro suberic acid, azelaic acid Diacid, sebacic acid, hexadecanedioic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid Acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, icosanedioic acid, behenicanedioic acid, trichosanedioic acid, twenty-four Alkanedioic acid, pentacosanedioic acid, hexadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triaconanedioic acid, tridecanedioic acid Acids, tridodecanedioic acid, diethylene glycol acid, and dicarboxylic acids represented by the following formulas, etc. are further exemplified.

（式中，Z表示碳數1～6的烴基，n表示1～6的整數。）[Chemical formula 15]

(In the formula, Z represents a hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer of 1 to 6.)

As the dicarboxylic acid containing an aromatic group, the dicarboxylic acid having the following aromatic group is preferable, and the dicarboxylic acid composed only of the following aromatic group and two COOH is more preferable.

式中，A表示選自包含-CH₂ -、-O-、-S-、-SO₂ -、-CO-、-NHCO-、-C（CF₃ ）₂ -及-C（CH₃ ）₂ -之組中之2價基。[Chemical formula 16]

In the formula, A represents selected from -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -and -C(CH ₃ ) ₂ -The divalent base in the group.

As specific examples of dicarboxylic acids containing aromatic groups, 4,4'-carbonyldibenzoic acid and 4,4'-dicarboxydiphenyl ether terephthalic acid are preferred.

In formula (3), R ¹²² represents a tetravalent organic group. ^{As a tetravalent organic group, the group demonstrated by R 22} in said formula (1) is mentioned, and the preferable range is also the same.

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. In addition, the number average molecular weight (Mn) is preferably 7200 to 14000, more preferably 8000 to 12000, and even more preferably 9200 to 11200. The dispersion degree of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the degree of dispersion of the polybenzoxazole precursor is not particularly limited. For example, it is preferably 2.6 or less, more preferably 2.5 or less, more preferably 2.4 or less, more preferably 2.3 or less, and 2.2 or less It is even better.

式（X）中，R¹³³ 表示2價有機基，R¹³⁴ 表示4價有機基。(Polybenzoxazole) The polybenzoxazole may be a compound having a benzoxazole ring, and it is not particularly limited, but a compound having a repeating unit represented by the following formula (X) is preferred. It is a compound represented by the following formula (X), and a compound having a radical polymerizable group is more preferable. As the radical polymerizable group, the radical polymerizable group described with the polyimide precursor mentioned above is mentioned, and the preferable range is also the same. [Chemical formula 17]

In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group.

式（X-1）中，R¹³⁵ 及R¹³⁶ 中的至少一個是自由基聚合性基，另一個是有機基，且其他基團的定義與式（X）相同。 式（X-2） [化學式19]

式（X-2）中，R¹³⁷ 是自由基聚合性基，其他為取代基，且其他基團的定義與式（X）相同。When the polybenzoxazole has a radical polymerizable group, a radical polymerizable group may be ^{introduced into at least one of R 133} and R ¹³⁴ , as shown in the following formula (X-1) or formula (X-2) It is shown that a radical polymerizable group can be introduced at the end of the polybenzoxazole. Formula (X-1) [Chemical formula 18]

In formula (X-1), ^{at least one of R 135} and R ¹³⁶ is a radical polymerizable group, the other is an organic group, and the definition of the other groups is the same as that of formula (X). Formula (X-2) [Chemical Formula 19]

In the formula (X-2), ^R137 is a radically polymerizable group, the others are substituents, and the definitions of the other groups are the same as in the formula (X).

Examples of the divalent organic group represented by R ^{133 include aliphatic or aromatic groups. As a specific example, the group illustrated by R 121} of the formula (3) of the polybenzoxazole precursor is mentioned, and the preferred range is also the same.

As the tetravalent organic group represented by R ^{134 , the group described with R 122} in the formula (3) of the polybenzoxazole precursor is exemplified, and the preferred range is also the same.

Polybenzoxazole may not only contain the repeating structural unit represented by the above formula (X) which is based on one type of R ¹³³ or R ^{134 , but also may contain two or more different kinds of R 133} or R ¹³⁴ which are derived from the above The repeating structural unit represented by formula (X). Moreover, in addition to the repeating unit of the above formula (X), the polybenzoxazole may contain other types of repeating structural units.

Polybenzoxazole, for example, is obtained by reacting a diaminophenol derivative with the following compound to obtain a polybenzoxazole precursor, and then oxazolyizing it by a known oxazolation reaction method. The compound is selected From the dicarboxylic acid containing R ¹³³ and the dicarboxylic acid dichloride and dicarboxylic acid derivative of the above-mentioned dicarboxylic acid. In addition, in the case of a dicarboxylic acid, in order to increase the reaction yield, an active ester-type dicarboxylic acid derivative obtained by pre-reacting 1-hydroxy-1,2,3-benzotriazole and the like can be used.

The weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain a cured film with excellent mechanical properties, the weight average molecular weight is more preferably 20,000 or more. In addition, when there are two or more polybenzoxazoles, the weight average molecular weight of at least one polybenzoxazole is preferably in the above-mentioned range.

<<radical polymerizable compound>> The resin composition in the present invention may further contain a radical polymerizable compound. By containing a radically polymerizable compound, a negative photosensitive resin composition can be preferably used. Furthermore, a cured film with more excellent heat resistance can be formed. As the radically polymerizable compound, a compound having an ethylenically unsaturated bond is preferred, and a compound containing two or more groups having an ethylenic unsaturated bond is more preferred. The radical polymerizable compound may be any of chemical forms such as monomers, prepolymers, oligomers, mixtures thereof, and multimers thereof. As the group having an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth)acryloyl group, and a (meth)allyl group are preferable, and a (meth)acryloyl group is more preferable. In addition, the radically polymerizable compound in the present invention is a component different from the above-mentioned resin. That is, a polyimide precursor having a radically polymerizable group, a polyimide having a radically polymerizable group, a polybenzoxazole precursor having a radically polymerizable group, and a radically polymerizable group The polybenzoxazole is equivalent to resin.

In the present invention, the monomer-type radical polymerizable compound (hereinafter, also referred to as a radical polymerizable monomer) is a compound different from the polymer compound. The radical polymerizable monomer is typically a low-molecular compound, and a low-molecular compound having a molecular weight of 2000 or less is preferable, a low-molecular compound having a molecular weight of 1500 or less is more preferable, and a low-molecular compound having a molecular weight of 900 or less is even more preferable. In addition, the molecular weight of the radically polymerizable monomer is usually 100 or more. In addition, the oligomer type radical polymerizable compound is typically a polymer with a relatively low molecular weight, and a polymer formed by bonding 10 to 100 radical polymerizable monomers is preferred. As the molecular weight, the weight average molecular weight in terms of polystyrene by the gel permeation chromatography (GPC) method is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and more preferably 2,000 to 10,000.

The number of functional groups of the radically polymerizable compound in the present invention refers to the number of radically polymerizable groups in one molecule. From the standpoint of resolution, the resin composition preferably contains at least one bifunctional or more radically polymerizable compound containing two or more radically polymerizable groups, and at least one 2-4 functional radically polymerizable compound is Better.

Examples of the radically polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters and amides thereof. Esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reactants of unsaturated carboxylic acid esters or amides with monofunctional or polyfunctional isocyanates or epoxy groups with affinity substituents such as hydroxyl groups, amine groups, sulfhydryl groups, etc., and monofunctional Dehydration condensation reaction product of functional or polyfunctional carboxylic acid, etc. In addition, addition reactants of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and mercaptans, and halogen groups or toluene Substitution reactants of unsaturated carboxylic acid esters or amides having detachable substituents such as sulfonyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. As another example, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds substituted with unsaturated phosphonic acid, vinyl benzene derivatives such as styrene, vinyl ether, allyl ether, and the like can be used. As a specific example, the descriptions in paragraphs 0113 to 0122 of JP 2016-027357 A can be referred to, and these contents can be incorporated into this specification.

As the radically polymerizable compound, a compound having a boiling point of 100°C or higher under normal pressure is also preferable. As examples, polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate (Neopentyl glycol di(meth) acrylate, Pentaerythritol(meth)acrylate, Pentaerythritol(meth)acrylate, Dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, Dipentaerythritol(meth)acrylate Alcohol (meth)acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trimethylolethane, etc. Compounds that are (meth)acrylated by adding ethylene oxide or propylene oxide to functional alcohols, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, Japanese Patent Application Publication No. 51-37193 (Meth) acrylic urethanes described in Japanese Patent Publication No. 48-64183, Japanese Japanese Patent Publication No. 49-43191, and Japanese Patent Application Publication No. 52-30490 Acrylates, epoxy acrylates and other polyfunctional acrylates or methacrylates, which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also preferable.

As the radically polymerizable compound, the compounds described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, Japanese Patent No. 4364216, etc. having a stilbene ring and having two or more containing Compounds with ethylenically unsaturated bonds or cardo resins. Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-43946, Japanese Patent Publication No. 1-40337, Japanese Patent Publication No. 1-40336, and Japanese Patent Application Publication No. 2- Vinyl phosphonic acid compounds and the like described in the Gazette No. 25493. In addition, the perfluoroalkyl group-containing compound described in JP 61-22048 A can also be used. Furthermore, it is also possible to use those introduced as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984).

In addition to the above, compounds represented by the following general formulas (MO-1) to (MO-5) can also be preferably used. In addition, in the formula, when T is an oxyalkylene group, the end on the carbon atom side is bonded to R.

[Chemical formula 20]

[Chemical formula 21]

In each of the above formulas, n is an integer of 0-14, and m is an integer of 0-8. A plurality of R and T in the molecule may be the same or different. In each of the compounds represented by the above-mentioned formulas (MO-1)～(MO-5), at least one of the plurality of R means that it is represented by -OC(=O)CH=CH ₂ or -OC(=O)C (CH ₃ )=CH ₂ represents a group. Specific examples of the compounds represented by the above formulas (MO-1) to (MO-5) include the compounds described in paragraphs 0248 to 0251 of JP 2007-269779 A.

In addition, the following compounds described as formula (1) and formula (2) together with specific examples in Japanese Patent Laid-Open No. 10-62986 can also be used as radically polymerizable compounds, which are added to polyfunctional alcohols A compound obtained by (meth)acrylic acid esterification after ethylene oxide or propylene oxide. Furthermore, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used as a radically polymerizable compound, and these contents are incorporated in this specification.

As a radically polymerizable compound, dipentaerythritol triacrylate (as a commercial product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product is KAYARAD D-320; Nippon Kayaku Co., Ltd. product, A-TMMT: Shin-Nakamura Chemical Co., Ltd. product), dipentaerythritol penta(meth)acrylate (as commercially available product is KAYARAD D-310; Nippon Kayaku Co., Ltd. . System), dipentaerythritol hexa(meth)acrylate (as a commercially available product is KAYARAD DPHA; Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and these The structure in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue is preferred. It is also possible to use their oligomer types. Moreover, as a preferable example, the pentaerythritol derivatives and/or dipentaerythritol derivatives of the above-mentioned formula (MO-1) and (MO-2) can also be cited. In addition, SR209 manufactured by Sartomer company Inc. can also be used.

The radically polymerizable compound may have acid groups such as a carboxyl group, a sulfo group, and a phosphoric acid group. Examples of commercially available products include M-510 and M-520 which are polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., LTD. The preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. If the acid value of the above-mentioned compound is in the above-mentioned range, the manufacturing and handling properties are excellent, and furthermore, the developability is excellent. In addition, the radical polymerizability is good.

As the radically polymerizable compound, a compound having a caprolactone structure can also be used. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. Ε-Hexyl propane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylol melamine and other polyols are esterified with (meth)acrylic acid and ε-caprolactone. Lactones modify multifunctional (meth)acrylates. Among them, compounds represented by the following formula (C) are preferred.

Formula (C) [Chemical Formula 22]

In the formula, all 6 Rs are groups represented by the following formula (D), or 1 to 5 of the 6 Rs are groups represented by the following formula (D), and the remainder are represented by the following formula ( E) The group indicated.

Formula (D) [Chemical formula 23]

In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents 1 or 2, and "*" represents a bonding bond.

Formula (E) [Chemical Formula 24]

In the formula, R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bonding bond.

Compounds with this caprolactone structure are commercially available as KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and DPCA-20 (in the above formulas (C) to (E), m=1, The number of groups represented by formula (D) = 2, R ¹ is a compound of hydrogen atoms), DPCA-30 (in the above formula, m = 1, the number of groups represented by formula (D) = 3, R ¹ is a hydrogen atom compound), DPCA-60 (in the above formula, m=1, the number of groups represented by formula (D) = 6, R ¹ is a hydrogen atom compound), DPCA-120 ( in the above formula m = 2, the number of the group represented by the formula (D) = 6, R ¹ are both hydrogen atoms) and the like.

As the radically polymerizable compound, at least one selected from the group of compounds represented by the following general formula (i) or (ii) is also preferred.

[Chemical formula 25]

In formulas (i) and (ii), E each independently represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, y each independently represents An integer of 0-10, and X each independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxyl group. In formula (i), the total of (meth)acrylic groups is 3 or 4, m each independently represents an integer of 0-10, and the total of each m is an integer of 0-40. However, when the total of each m is 0, any one of X is a carboxyl group. In formula (ii), the total of (meth)acryloyl groups is 5 or 6, n each independently represents an integer of 0-10, and the total of each n is an integer of 0-60. However, when the total of each n is 0, any one of X is a carboxyl group.

In formula (i), m is preferably an integer of 0-6, and more preferably an integer of 0-4. Moreover, it is preferable that the total of each m is an integer of 2-40, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable. In formula (ii), n is preferably an integer of 0-6, and more preferably an integer of 0-4. Moreover, it is preferable that the total of each n is an integer of 3-60, the integer of 3-24 is more preferable, and the integer of 6-12 is especially preferable. In formula (i) or formula (ii) -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- is the end of the oxygen atom side bonded with X The form is better. In particular, in formula (ii), it is preferable that the six Xs are all acryloyl groups.

As commercially available products of the compounds represented by formula (i) and formula (ii), for example, SR-494, Nippon Kayaku Co., which is a 4-functional acrylate having 4 ethylene oxide chains, manufactured by Sartomer Company Inc., DPCA-60 as a 6-functional acrylate with 6 pentene oxide chains, TPA-330 as a tri-functional acrylate with 3 methacrylate chains, etc. manufactured by Ltd.

As a radically polymerizable compound, there are carbamates described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Application Publication No. 2-16765 Ethyl acrylates, ethylene oxide described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 Carbamate compounds that form a skeleton are also preferred. In addition, it is also possible to use additions described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. 1-105238 that have an amino group structure or a thioether structure in the molecule. Into polymerizable monomers. Commercial products include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As the radically polymerizable compound, it is preferable to have a partial structure represented by the following formula from the viewpoint of heat resistance. Among them, * in the formula is the connecting key.

[Chemical formula 26]

As specific examples of the compound having the above partial structure, for example, trimethylolpropane tri(meth)acrylate, isocyanuric acid ethylene oxide modified di(meth)acrylate, isocyanuric acid ring Oxyethane modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate ) Acrylate, dipentaerythritol hexa(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, etc.

In the resin composition, from the viewpoint of good radical polymerizability and heat resistance, the content of the radical polymerizable compound is preferably 1 to 50% by mass relative to the total solid content of the resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. In addition, the mass ratio of resin (preferably polyimide precursor) to radical polymerizable compound (resin/polyimide precursor/radical polymerizable compound) is preferably 98/2 to 10/90 , 95/5-30/70 is more preferable, and 90/10-50/50 is still more preferable. If the mass ratio of the resin and the radically polymerizable compound is in the above range, a cured film with more excellent curability and heat resistance can be formed. Only one type of radical polymerizable compound may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above-mentioned range.

<<Photopolymerization initiator>> The resin composition in the present invention preferably contains a photopolymerization initiator. As the photopolymerization initiator, a photocationic polymerization initiator, a photoradical polymerization initiator, etc. can be cited, and a photoradical polymerization initiator is preferred. The resin composition of the present invention contains a photo-radical polymerization initiator, and after the resin composition is applied to a substrate such as a semiconductor wafer to form a resin composition layer, light is irradiated to cause damage caused by the generated free radicals. By hardening, the solubility in the light-irradiated part can be reduced. Therefore, for example, there is an advantage that by exposing the resin composition layer through a light mask having a pattern that only shields the electrode portion, regions with different solubility can be easily produced depending on the pattern of the electrode or the like.

The photopolymerization initiator is not particularly limited, and it can be appropriately selected from known photopolymerization initiators. For example, a photopolymerization initiator having photosensitivity to light from the ultraviolet region to the visible region is preferred. In addition, it can be an active agent that generates active free radicals by interacting with a light-excited sensitizer. The photopolymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) and an ethyl acetate solvent are used, and the measurement is preferably performed at a concentration of 0.01 g/L.

As a photopolymerization initiator, a well-known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl skeleton), phosphine compounds such as phosphine oxides, and hexaarylbisimidazole , Oxime derivatives and other oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, Metallocene compounds, organoboron compounds, iron arene complexes, etc. Regarding these details, reference can be made to the description in paragraphs 0165 to 0182 of JP 2016-027357 A, and the contents are incorporated into this specification. In addition, as the ketone compound, for example, the compound described in paragraph 0087 of JP 2015-087611 A can be exemplified, and the content is incorporated in this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photopolymerization initiator, α-hydroxyketone compounds, α-aminoketone compounds, phosphine compounds, and metallocene compounds can also be preferably used. More specifically, for example, the photopolymerization initiator described in Japanese Patent Laid-Open No. 10-291969 and the photopolymerization initiator described in Japanese Patent No. 4225898 can also be used. As the α-hydroxy ketone compound, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (brand names: all manufactured by BASF) can be used. As the α-amino ketone compound, commercially available IRGACURE-907, IRGACURE-369, and IRGACURE-379 (brand names: all manufactured by BASF Corporation) can be used. As the α-amino ketone compound, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 whose absorption maximum wavelength is matched to a wavelength light source such as 365 nm or 405 nm can also be used. Examples of the phosphine compound include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. In addition, IRGACURE-819 or IRGACURE-TPO (brand name: both manufactured by BASF Corporation), which are commercially available products, can be used. As the metallocene compound, IRGACURE-784 (manufactured by BASF Corporation) and the like can be exemplified.

As a photopolymerization initiator, an oxime compound is more preferable. By using an oxime compound, the exposure latitude can be more effectively improved. The oxime compound has a wide exposure latitude (exposure margin) and also functions as a hot alkali generator, so it is particularly preferred. As specific examples of the oxime compound, the compounds described in JP 2001-233842, the compounds described in JP 2000-80068, and the compounds described in JP 2006-342166 can be used. . As a preferable oxime compound, for example, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxy Aminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzyl Oxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyloxyimino-1 -Phenylpropan-2-one, etc.

Among the commercially available products, IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE03, IRGACURE OXE04 (the above are made by BASF), ADEKA OPTOMER N-1919 (made by ADEKA CORPORATION, Japanese Patent Application Publication No. 2012-14052 Recorded photopolymerization initiator 2). In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. Also, DFI-091 (DAITO) can be used. Manufactured by CHEMIX Co., Ltd.). Furthermore, oxime compounds having a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in JP 2010-262028 A and JP 2014 -Compounds 24, 36-40 described in paragraph 0345 of JP-A-500852, compound (C-3) described in paragraph 0101 of JP 2013-164471 A, etc. As the best oxime compound, exemplified The oxime compound having a specific substituent shown in JP 2007-269779 A, the oxime compound having a sulfur aryl group shown in JP 2009-191061, and the like.

The photopolymerization initiator is selected from the group consisting of trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and phosphine compounds from the viewpoint of exposure sensitivity. , Phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene- At least one of iron complexes and their salts, halomethyl oxadiazole compounds and 3-aryl substituted coumarin compounds is preferably selected from trihalomethyl triazine compounds, α-hydroxy ketone compounds, α -At least one of aminoketone compounds, phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds is more preferred , At least one selected from the group consisting of trihalomethyl triazine compounds, α-hydroxy ketone compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers and benzophenone compounds is further preferred. The metallocene A compound or an oxime compound is further preferred, and an oxime compound is particularly preferred.

式（I）中，R⁵⁰ 為碳數1～20的烷基；被一個以上的氧原子中斷之碳數2～20的烷基；碳數1～12的烷氧基；苯基；碳數1～20的烷基、碳數1～12的烷氧基、鹵素原子、環戊基、環己基、碳數2～12的烯基、被一個以上的氧原子中斷之碳數2～18的烷基及被碳數1～4的烷基中的至少一個取代之苯基；或聯苯基，R⁵¹ 為由式（II）表示之基團，或者是與R⁵⁰ 相同的基團。R⁵² ～R⁵⁴ 各自獨立地為碳數1～12的烷基、碳數1～12的烷氧基或鹵素。 [化學式28]

式中，R⁵⁵ ～R⁵⁷ 與上述式（I）的R⁵² ～R⁵⁴ 相同。In addition, the photopolymerization initiator can also use N,N'-tetraalkanes such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Michelone). -4,4'-diaminobenzophenone; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl- Aromatic ketones such as 1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1; quinones formed by condensation with aromatic rings such as alkylanthraquinones; benzoin alkyl ethers, etc. Benzoin ether compounds, benzoin, alkyl benzoin and other benzoin compounds; benzyl dimethyl ketal and other benzoin derivatives, etc. In addition, a compound represented by the following formula (I) can also be used. [Chemical formula 27]

In formula (I), R ⁵⁰ is an alkyl group having 1 to 20 carbons; an alkyl group having 2 to 20 carbons interrupted by more than one oxygen atom; an alkoxy group having 1 to 12 carbons; a phenyl group; Alkyl groups of 1 to 20, alkoxy groups of 1 to 12 carbons, halogen atoms, cyclopentyl, cyclohexyl, alkenyl groups of 2 to 12 carbons, 2 to 18 carbons interrupted by more than one oxygen atom An alkyl group and a phenyl group substituted with at least one of an alkyl group having 1 to 4 carbon atoms; or a biphenyl group, where R ⁵¹ is a group represented by formula (II), or the same group as ^{R 50.} R ⁵² to R ⁵⁴ are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or halogen. [Chemical formula 28]

In the formula, R ⁵⁵ to R ⁵⁷ are the same as ^{R 52} to R ^{54 in the} above formula (I).

In addition, as the photopolymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication WO2015/125469 can also be used.

The content of the photopolymerization initiator is preferably 0.1 to 30% by mass relative to the total solid content of the resin composition, more preferably 0.1 to 20% by mass, and still more preferably 0.1 to 10% by mass. The photopolymerization initiator may contain only one type, or two or more types. When two or more kinds of photopolymerization initiators are contained, it is preferable that the total thereof is in the above-mentioned range.

<<Polymerization inhibitor>> The resin composition in the present invention preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, p-tert-butylcatechol, p- Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl-6 -Tertiary butyl phenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-Cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso -N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tertiarybutyl)phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compound described in paragraphs 0031 to 0046 of International Publication WO2015/125469 can also be used.

When the resin composition has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the resin composition. There may be only one type of polymerization inhibitor, or two or more types. When there are two or more kinds of polymerization inhibitors, it is preferable that the sum total is the above-mentioned range.

<<Photobase generator>> The resin composition in the present invention may contain a photobase generator. Photobase generators are those that generate alkali by exposure and do not show activity under normal conditions of normal temperature and pressure. However, if they generate alkali (alkaline substances) when exposed to electromagnetic waves and heating as an external stimulus, they do not Specially limited. The base generated by exposure functions as a catalyst when the polyimide precursor is cured by heating, and therefore can be preferably used in a negative photosensitive resin composition.

The content of the photobase generator is not particularly limited as long as it can form a desired pattern, and can be set to a normal content. The content of the photobase generator relative to 100 parts by mass of the resin composition is preferably in the range of 0.01 parts by mass or more and less than 30 parts by mass, more preferably in the range of 0.05 parts by mass to 25 parts by mass, and more than 0.1 parts by mass It is more preferable to be in the range of -20 parts by mass.

In the present invention, a known compound can be used as the photobase generator. For example, it can be listed in M. Shirai, and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Kadooka Masahiro, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol., 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol., 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol., 19, 81 (2006), as described in transition metal compound complexes , Those with structures such as ammonium salts, such as those where the amidine moiety is latent due to the formation of salts with carboxylic acids, ionic compounds whose alkali components are neutralized by the formation of salts, urethane derivatives, and oxime ester derivatives , Amino compounds and other nonionic compounds in which alkali components are latentized by urethane bonds or oxime bonds. In addition, it is also preferable to use WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd.).

The basic substance generated by the photobase generator is not particularly limited, and compounds having an amine group are exemplified. In particular, polyamines such as monoamines and diamines, or amidines are exemplified. The alkaline substance produced is preferably a compound having a higher basicity amine group. The reason for this is that it has a strong catalytic effect on the dehydration condensation reaction and the like in the imidization of the polyimide precursor, and a small amount can be added to express the catalytic effect in the dehydration condensation reaction and the like at a lower temperature. That is, the generated alkaline substance has a large catalytic effect, so the sensitivity of the appearance as a resin composition is improved. From the viewpoint of the above-mentioned catalytic effect, amidine and aliphatic amine groups are preferred.

The photobase generator is preferably a photobase generator that does not contain a salt in the structure. It is preferable that there is no charge on the nitrogen atom of the base portion generated in the photobase generator. In photobase generators, the base produced is potentially better by using a covalent bond. The mechanism for producing the base is that the covalent bond between the atom adjacent to the nitrogen atom of the base part is A compound that generates a base by cutting is more preferable. If it is a photobase generator that does not contain a salt in the structure, the photobase generator can be neutralized, so the solvent solubility is good, and the pot life is improved. For these reasons, it is preferable that the amine produced by the photobase generator used in the present invention is a primary amine or a secondary amine.

In addition, from the above-mentioned reasons, among the photobase generators, the base produced as described above is preferably latentized using a covalent bond. In addition, it is more preferable to use an amide bond, a urethane bond, or an oxime bond for the generated base.

As the photobase generator, the photobase generator having a cinnamic acid amide structure described in JP 2009-80452 and International Publication WO2009/123122, JP 2006-189591 and Japan can also be used. The photobase generator having a urethane structure described in JP 2008-247747 A, the oxime ester structure described in JP 2007-249013 and JP 2008-003581, A photobase generator of carbamethoxime structure.

In addition, examples of photobase generators include the compounds described in paragraphs 0185-0188, 0199-0200, and 0202 of JP 2012-93746 A, and paragraphs 0022 to 0069 of JP 2013-194205. The compound described in JP 2013-204019, the compound described in paragraphs 0026 to 0074, and the compound described in paragraph 0052 of WO2010/064631.

<<Thermal base generator>> The resin composition in the present invention may contain a thermal base generator. As a thermal base generator, a thermal base generator containing at least one selected from the group consisting of acidic compounds (A1) that generate bases when heated to above 40°C, and anions of 0-4 with pKa1 and ammonium salts of ammonium cations (A2) For better. _{Here, pKa1 represents the logarithmic display (-Log 10} Ka) of the dissociation constant (Ka) of the first proton of the polybasic acid. The acidic compound (A1) and the ammonium salt (A2) are those that generate alkali when heated. Therefore, the alkali generated by these compounds can promote the cyclization reaction of polyimide precursors, etc., and can be used at low temperatures. Carry out the cyclization of polyimide precursors, etc. In addition, regarding these compounds, even if the polyimide precursors etc. which are cyclized and hardened by alkali coexist, the cyclization of the polyimide precursors etc. hardly progresses without heating, so the preparation and storage are stable. Resin composition with excellent properties. In addition, in this specification, an acidic compound refers to a compound with a pH value of less than 7 measured at 20°C using a pH meter. The solution is to collect 1g of the compound in a container and add 50mL of ion-exchanged water and tetrahydrofuran. The mixed solution (mass ratio of water/tetrahydrofuran = 1/4) and stirred at room temperature for 1 hour to obtain the solution.

The base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40°C or higher, and more preferably 120 to 200°C. The upper limit of the alkali generation temperature is more preferably 190°C or less, more preferably 180°C or less, and even more preferably 165°C or less. The lower limit of the alkali generation temperature is more preferably 130°C or higher, and more preferably 135°C or higher. If the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120° C. or higher, the alkali is unlikely to be generated during storage, so a resin composition with excellent stability can be prepared. If the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200° C. or lower, the cyclization temperature of the polyimide precursor can be lowered. The alkali generation temperature can be measured, for example, by using differential scanning calorimetry, heating the compound to 250°C at 5°C/min in a pressure-resistant capsule, and reading the peak temperature of the heating peak at the lowest temperature, and measuring the peak The temperature is used as the alkali generation temperature.

The base produced by the thermal base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. The tertiary amine has high basicity, so it can further reduce the cyclization temperature of the polyimide precursor. In addition, the boiling point of the alkali produced by the thermal alkali generator is preferably 80°C or higher, more preferably 100°C or higher, and most preferably 140°C or higher. In addition, the molecular weight of the base produced is preferably 80 to 2,000. It is more preferable that the lower limit is 100 or more. The upper limit is more preferably 500 or less. In addition, the value of molecular weight is a theoretical value obtained from the structural formula.

The acidic compound (A1) preferably contains one or more selected from the group consisting of an ammonium salt and a compound represented by the formula (A1) described later.

The above-mentioned ammonium salt (A2) is preferably an acidic compound. In addition, the above-mentioned ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40°C or higher (preferably 120 to 200°C), or it may be a compound containing an acidic compound that generates a base when heated to 40°C or higher (preferably 120 to 200°C). ℃) when it produces compounds other than the acidic compounds of the base.

上述式中，R¹ ～R⁶ 分別獨立地表示氫原子或烴基，式R⁷ 表示烴基。R¹ 與R² 、R³ 與R⁴ 、R⁵ 與R⁶ 、R⁵ 與R⁷ 可以分別鍵結而形成環。In the present invention, the ammonium salt refers to a salt of an ammonium cation and an anion represented by the following formula (101) or formula (102). The anion may be bonded to any part of the ammonium cation via a covalent bond, or it may be present outside the molecule of the ammonium cation, and it is preferable to have it outside the molecule of the ammonium cation. In addition, having an anion outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded by a covalent bond. Hereinafter, the anion outside the molecule of the cation part is referred to as a counter anion. [Chemical formula 29]

In the above formula, R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and the formula R ⁷ represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁵ and R ⁷ may be respectively bonded to form a ring.

In the present invention, it is preferable that the ammonium salt has an anion having a pKa1 of 0 to 4 and an ammonium cation. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and more preferably 3.2 or less. The lower limit is more preferably 0.5 or more, and more preferably 1.0 or more. If the pKa1 of the anion is in the above range, the polyimide precursor or the like can be cyclized at a low temperature, and the stability of the resin composition can be improved. If pKa1 is 4 or less, the stability of the thermal alkali generator is good, the generation of alkali without heating can be suppressed, and the stability of the resin composition is good. If pKa1 is 0 or more, the generated alkali is not easily neutralized, and the cyclization efficiency of the polyimide precursor and the like is good. The type of anion is preferably one selected from the group consisting of carboxylate anion, phenol anion, phosphate anion, and sulfate anion, and carboxylate anion is more preferred from the viewpoint of compatibility of salt stability and thermal decomposition. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion. The carboxylate anion is preferably an anion of a divalent or more carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, it can be used as a thermal alkali generator which can further improve the stability, curability, and developability of the resin composition. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the resin composition can be further improved. In the present invention, the carboxylate anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. It is more preferable that pKa1 is 3.5 or less, and it is still more preferable that it is 3.2 or less. According to this aspect, the stability of the resin composition can be further improved. Among them, pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid, and can refer to Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod) , FC; Editor: Braude, EA, Nachod, FC; Academic Press, New York, 1955), Data for Biochemical Research (Physical Identification of Organic Structure) (Author: Dawson, RMC et al; Oxford, Clarendon Press, 1959) The value recorded in. For compounds not described in these documents, the value calculated by the structural formula using software using ACD/pKa (manufactured by ACD/Labs) is used.

式（X1）中，EWG表示吸電子基。In the present invention, the carboxylate anion is preferably represented by the following formula (X1). [Chemical formula 30]

In formula (X1), EWG represents an electron withdrawing group.

In the present invention, the electron withdrawing group refers to the one whose substituent constant σm of Hammett represents a positive value. Among them, σm is described in detail in Tono Yufu's general theory, "Organic Synthetic Chemistry Association Journal" Volume 23, No. 8 (1965) P.631-642. In addition, the electron withdrawing group of the present invention is not limited to the substituents described in the above-mentioned documents. Examples of substituents whose σm represents a positive value include CF ₃ groups (σm=0.43), CF ₃ CO groups (σm=0.63), HC≡C groups (σm=0.21), CH ₂ =CH groups (σm =0.06), Ac group (σm=0.38), MeOCO group (σm=0.37), MeCOCH=CH group (σm=0.21), PhCO group (σm=0.34), H ₂ NCOCH ₂ group (σm=0.06), etc. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

式中，R^x1 ～R^x3 分別獨立地表示氫原子、烷基、烯基、芳基、羥基或羧基，Ar表示芳基。In the present invention, EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6). [Chemical formula 31]

In the formula, R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxyl group, and Ar represents an aryl group.

式（X）中，L¹⁰ 表示單鍵或選自伸烷基、伸烯基、伸芳基、-NR^X -及它們的組合中之2價連結基，R^X 表示氫原子、烷基、烯基或芳基。In the present invention, it is also preferable that the carboxylate anion is represented by the following formula (X). [Chemical formula 32]

In formula (X), L ¹⁰ represents a single bond or a divalent linking group selected from alkylene, alkenylene, arylene, -NR ^X -and combinations thereof, R ^X represents a hydrogen atom, an alkyl group, Alkenyl or aryl.

Specific examples of the carboxylate anion include maleate anion, phthalate anion, N-phenyliminodiacetate anion, and oxalate anion. These can be used preferably.

The ammonium cation is preferably represented by any of the following general formulas (Y1-1) to (Y1-6). [Chemical formula 33]

In the above general formula, R ¹⁰¹ represents an n-valent organic group, R ¹⁰² to R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group, R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group, R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring, Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0-5.

R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ^108, and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring. Examples of the ring include aliphatic rings (non-aromatic hydrocarbon rings), aromatic rings, heterocyclic rings, and the like. The ring can be a single ring or multiple rings. As the linking group when the above-mentioned group is bonded to form a ring, it can be selected from the group consisting of -CO-, -O-, -NH-, divalent aliphatic group, divalent aryl group, and combinations thereof Divalent linking base. Specific examples of the formed ring include, for example, a pyrrolidine ring, a pyrrole ring, a piperidine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a morpholine ring, and a thiazine ring. Ring, indole ring, isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring, etc.

式（Y）中，Ar¹⁰ 表示芳香族基，R¹¹ ～R¹⁵ 分別獨立地表示氫原子或烴基，R¹⁴ 與R¹⁵ 可以彼此鍵結而形成環，n表示1以上的整數。In the present invention, the ammonium cation is preferably a structure represented by formula (Y1-1) or formula (Y1-2), represented by formula (Y1-1) or formula (Y1-2), and R ¹⁰¹ is an aryl group The structure is more preferable, represented by formula (Y1-1), and ^{the structure in which R 101} is an aryl group is particularly preferable. That is, in the present invention, it is more preferable that the ammonium cation is represented by the following formula (Y). [Chemical formula 34]

In formula (Y), Ar ¹⁰ represents an aromatic group, R ¹¹ to R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group, R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring, and n represents an integer of 1 or more.

R ¹¹ and R ¹² each independently represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group is not particularly limited, but an alkyl group, an alkenyl group, or an aryl group is preferred. R ¹¹ and R ¹² are preferably hydrogen atoms.

R ¹³ to R ¹⁵ represent a hydrogen atom or a hydrocarbon group. As the hydrocarbon group include the above-described R ^11, R ¹² described for the hydrocarbon. R ¹³ to R ^{15 are} particularly preferably alkyl groups, and the preferred aspects are the same as those described ^{with R 11} and R ^12.

R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. Examples of the ring include cycloaliphatic (non-aromatic hydrocarbon ring), aromatic ring, and heterocyclic ring. The ring can be a single ring or multiple rings. As ^{the linking group when R 14} and R ^{15 are} bonded to form a ring, it can be selected from the group consisting of -CO-, -O-, -NH-, divalent aliphatic group, divalent aromatic group, and combinations thereof The two-valent linking base in the middle. Specific examples of the formed ring include, for example, a pyrrolidine ring, a pyrrole ring, a piperidine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a morpholine ring, and a thiazine ring. Ring, indole ring, isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring, etc.

Among R ¹³ to R ¹⁵ , R ¹⁴ and R ¹⁵ are bonded to each other to form a ring, or R ¹³ is a linear alkyl group having 5 to 30 carbons (more preferably 6 to 18 carbons), and R ¹⁴ and R ¹⁵ are respectively The alkyl group independently having 1 to 3 carbon atoms (more preferably 1 or 2 carbon atoms) is preferred. According to this aspect, an amine species with a high boiling point can be easily produced. In addition, from the viewpoint of the basicity or boiling point of the amine species produced, ^{the total number of carbon atoms of R 13} , R ¹⁴ and R ¹⁵ is preferably 7-30, more preferably 10-20. In addition, in view of the fact that amine species with a high boiling point are likely to be generated, ^{the chemical formula weight of "-NR 13} R ¹⁴ R ¹⁵ "in the formula (Y) is preferably 80 to 2000, and more preferably 100 to 500.

In addition, as an embodiment for further improving the adhesion to a metal layer such as copper, it can be exemplified in formula (Y), where R ¹³ and R ¹⁴ are methyl or ethyl, and R ¹⁵ is a straight chain with 5 or more carbon atoms. , Branched or cyclic alkyl, in the form of aryl. R ¹³ and R ¹⁴ are methyl groups, and R ¹⁵ is preferably a linear alkyl group having 5 to 20 carbons, a branched alkyl group having 6 to 17 carbons, a cyclic alkyl group having 6 to 10 carbons, or a phenyl group. R ¹³ and R ¹⁴ are methyl groups, and R ¹⁵ is a linear alkyl group having 5 to 10 carbon atoms, a branched alkyl group having 6 to 10 carbon atoms, a cyclic alkyl group having 6 to 8 carbon atoms, or a phenyl group. By reducing the hydrophobicity of the amine species in this way, even when the amine is adhered to the metal layer such as copper, the affinity between the metal layer and the polyimide etc. can be improved.

In the present invention, it is also preferable that the acidic compound is a compound represented by the following formula (A1). The compound is acidic at room temperature, and the carboxyl group will be decarbonated or dehydrated and cyclized by heating, whereby the previously neutralized and deactivated amine site becomes active, thereby becoming basic. Hereinafter, the formula (A1) will be described.

於式（A1）中，A¹ 表示p價有機基，R¹ 表示1價有機基，L¹ 表示（m+1）價連結基，m表示1以上的整數，p表示1以上的整數。Formula (A1) [Chemical formula 35]

In formula (A1), A ¹ represents a p-valent organic group, R ¹ represents a monovalent organic group, L ¹ represents a (m+1) valent linking group, m represents an integer of 1 or more, and p represents an integer of 1 or more.

In the formula (A1), A ¹ represents a p-valent organic group. As the organic group, an aliphatic group, an aromatic group, etc. can be mentioned, and an aromatic group is preferred. By setting A ¹ as an aromatic group, a base with a high boiling point can be easily generated at a lower temperature. By increasing the boiling point of the alkali produced, the polyimide precursor can be prevented from being volatilized or decomposed by heating during hardening, and the polyimide precursor can be cyclized more effectively. As a monovalent aliphatic group, an alkyl group, an alkenyl group, etc. are mentioned, for example. The carbon number of the alkyl group is preferably 1-30, more preferably 1-20, and still more preferably 1-10. The alkyl group may be any of linear, branched, and cyclic. The alkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include methyl, ethyl, tertiary butyl, dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and the like. The carbon number of the alkenyl group is preferably 2-30, more preferably 2-20, and still more preferably 2-10. The alkenyl group may be any of linear, branched, and cyclic. The alkenyl group may have a substituent or may be unsubstituted. As an alkenyl group, a vinyl group, a (meth)allyl group, etc. are mentioned. Examples of the aliphatic group having a valence of two or more include groups obtained by removing one hydrogen atom from the above-mentioned monovalent aliphatic group. The aromatic group may be monocyclic or polycyclic. The aromatic group may be an aromatic heterocyclic group containing a hetero atom. The aromatic group may have a substituent or may be unsubstituted. Unsubstituted is better. Specific examples of aromatic groups include benzene ring group, naphthalene ring group, pentene ring group, indenyl ring group, azulene ring group, heptene ring group, indenene ring group, perylene ring group, and fused pentacene ring group. Cyclic group, acenaphthylene ring group, phenanthrene ring group, anthracyclyl group, condensed tetraphenyl ring group, tri-ring group, terphenylene ring group, stilbene ring group, biphenyl ring group, pyrrolyl ring group, furan ring group, thiophene Cyclic, imidazole, oxazole, thiazolyl, pyridine, pyrazine, pyrimidine, pyridazine, indolazine, indole, and benzofuran , Benzothiophene ring group, isobenzofuran ring group, quinazine ring group, quinoline ring group, phthalazine ring group, naphthyridinyl ring group, quinoxaline ring group, quinoxazoline ring group, isoquinoline Cyclic, carbazole ring, phenanthridinyl, acridine, phenanthroline, thioanthrane, benzopyran, xanthenyl, phenanthryl, phenanthrazine Group and phenazine ring group, phenyl ring group is the best. In the aromatic group, a plurality of aromatic rings may be connected via a single bond or a connecting group described later. As the linking group, for example, an alkylene group is preferable. It is also preferable that the alkylene group is either straight chain or branched. Specific examples of groups connected by a plurality of aromatic rings via single bonds or linking groups include biphenyl, diphenylmethane, diphenylpropanyl, diphenylisopropyl, and triphenylmethane. Group, tetraphenylmethane group, etc.

Examples of substituents that may have ^{an organic group represented by A 1} include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy group, ethoxy group, and tertiary butoxy group. Group; Aryloxy groups such as phenoxy and p-tolyloxy; Alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl; Aryloxycarbonyl groups such as phenoxycarbonyl; Acetyloxy, propionyloxy and Acetyl groups such as benzyloxy; acetyl group, benzyl group, isobutyryl group, acryloyl group, methacryloyl group and methacryloyl group; methyl mercapto group and tertiary butyl mercapto group Alkyl mercapto groups; aryl mercapto groups such as phenyl mercapto and p-tolyl mercapto; alkyl groups such as methyl, ethyl, tertiary butyl, and dodecyl; halogenated alkyl groups such as fluorinated alkyl groups; cyclopentyl, Cycloalkyl groups such as cyclohexyl, cycloheptyl and adamantyl; aryl groups such as phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthracenyl and phenanthryl; hydroxyl; carboxyl; formyl; Sulfo; Cyano; Alkylaminocarbonyl; Arylaminocarbonyl; Sulfonamide; Silyl; Amino; Monoalkylamino; Dialkylamino; Arylamino; Diarylamine Group; thiooxy; or a combination thereof.

L ¹ represents the (m+1) valence link base. The linking group is not particularly limited, and can be exemplified -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene (preferably carbon number 1 -10 linear or branched alkylene), cycloalkylene (preferably a cycloalkylene having 3 to 10 carbons), alkenylene (preferably a linear or branched alkenylene having 210 carbons) ) Or the connecting base formed by connecting them in plural. The total carbon number of the linking group is preferably 3 or less. The linking group is preferably an alkylene group, a cycloalkylene group, or an alkenylene group, a straight-chain or branched alkylene group is more preferred, a straight-chain alkylene group is further preferred, and an ethylene group or a methylene group is particularly preferred. , Methylene is the best.

R ¹ represents a monovalent organic group. As a monovalent organic group, aliphatic group, aromatic group, etc. are mentioned. Regarding the aliphatic group and the aromatic group, those described with the above-mentioned A ¹ can be cited. The monovalent organic group represented by R ¹ may have a substituent. As a substituent, the above-mentioned can be mentioned. R ¹ is preferably a group having a carboxyl group. That is, R ¹ is preferably a group represented by the following formula. -L ² -(COOH) _{n In the} formula, L ² represents a (n+1) valent linking group, and n represents an integer of 1 or more. Regarding the linking group represented by L ² , the groups described with the above L ¹ can be cited, and the preferred ranges are also the same. Ethylene or methylene is particularly preferred, and methylene is most preferred. n represents an integer of 1 or more, 1 or 2 is preferable, and 1 is more preferable. The upper limit of n is the maximum number of substituents that the linking group represented ^{by L 2 can adopt.} If n is 1, heating at 200°C or less will easily produce a tertiary amine with a high boiling point. Furthermore, the stability of the resin composition can be improved.

m represents an integer of 1 or more, 1 or 2 is preferable, and 1 is more preferable. The upper limit of m is the maximum number of substituents that the linking group represented ^{by L 1 can adopt.} If m is 1, heating at 200° C. or lower is likely to produce a tertiary amine with a high boiling point. Furthermore, the stability of the resin composition can be improved. p represents an integer of 1 or more, 1 or 2 is preferable, and 1 is more preferable. The upper limit of p is the maximum number of substituents that can be used for the organic group represented ^{by A 1.} If p is 1, heating at 200° C. or lower is likely to produce a tertiary amine with a high boiling point.

式（1a）中，A¹ 表示p價有機基，L¹ 表示（m+1）價連結基，L² 表示（n+1）價連結基，m表示1以上的整數，n表示1以上的整數，p表示1以上的整數。 通式（1a）的A¹ 、L¹ 、L² 、m、n及p的定義與以通式（A1）進行說明之範圍相同，較佳範圍亦相同。In the present invention, the compound represented by the formula (A1) is preferably a compound represented by the following formula (1a). [Chemical formula 36]

In formula (1a), A ¹ represents a p-valent organic group, L ¹ represents a (m+1) valence linking group, L ² represents a (n+1) valence linking group, m represents an integer of 1 or more, and n represents 1 or more Integer, p represents an integer of 1 or more. ^{The definitions of A 1} , L ¹ , L ² , m, n, and p in the general formula (1a) are the same as those described in the general formula (A1), and the preferred ranges are also the same.

In the present invention, the compound represented by the formula (A1) is preferably N-aryliminodiacetic acid. N-aryliminodiacetic acid is a compound in which A ¹ in the general formula (A1) is an aromatic group, L ¹ and L ² are methylene groups, m is 1, n is 1, and p is 1. N-Aryliminodiacetic acid is prone to produce tertiary amines with high boiling points at 120-200°C.

Hereinafter, specific examples of the thermal alkali generator are described, but the present invention is not limited to these. These can be used individually or in mixture of two or more types, respectively. Me in the following formula represents a methyl group. Among the compounds shown below, (A-1) to (A-11), (A-18), and (A-19) are compounds represented by the above formula (A1). Among the compounds shown below, (A-1)～(A-11), (A-18)～(A-26) are more preferable, (A-1)～(A-9), (A-18) ) To (A-21), (A-23), (A-24) are further preferred.

[Table 1]

[表3]

[表4]

[表5]

[Table 2]

[table 3]

[Table 4]

[table 5]

As the thermal base generator used in the present invention, the compounds described in paragraphs 0015 to 0055 of the specification of Japanese Patent Application No. 2015-034388 can also be preferably used, and these contents are incorporated in this specification.

When a thermal base generator is used, the content of the thermal base generator in the resin composition is preferably 0.1 to 50% by mass relative to the total solid content of the resin composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. One kind or two or more kinds of thermal base generators can be used. When two or more are used, the total amount is preferably in the above-mentioned range.

<<Thermal radical polymerization initiator>> The resin composition in the present invention may contain a thermal radical polymerization initiator. As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used. The thermal radical polymerization initiator is a compound that generates free radicals by heat energy and initiates or promotes the polymerization reaction of the polymerizable compound. By adding a thermal radical polymerization initiator, when the cyclization reaction of the polyimide precursor proceeds, the polymerization reaction of the polymerizable compound and the like can be performed. In addition, when the polyimide precursor contains a radically polymerizable group, the polymerization reaction of the polyimide precursor can be performed simultaneously with the cyclization of the polyimide precursor, so that higher heat resistance can be achieved. Examples of thermal radical polymerization initiators include aromatic ketones, onium salt compounds, peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, and metallocenes. Compounds, active ester compounds, compounds with carbon halogen bonds, azo compounds, etc. Among them, peroxides or azo compounds are more preferred, and peroxides are particularly preferred. The 10-hour half-life temperature of the thermal radical polymerization initiator used in the present invention is preferably 90-130°C, more preferably 100-120°C. Specifically, the compounds described in paragraphs 0074 to 0118 of JP 2008-63554 A can be cited. Among the commercially available products, PERBUTYL Z and PERCUMYLD (manufactured by NOF CORPORATION) can be preferably used.

When the resin composition contains a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator relative to the total solid content of the resin composition is preferably 0.1-50% by mass, more preferably 0.1-30% by mass , 0.1-20% by mass is particularly preferred. Moreover, it is preferable to contain 0.1-50 mass parts of thermal radical polymerization initiators with respect to 100 mass parts of polymerizable compounds, and it is more preferable to contain 0.5-30 mass parts. According to this aspect, it is easy to form a cured film with more excellent heat resistance. There may be only one kind of thermal radical polymerization initiator, or two or more kinds. When there are two or more thermal radical polymerization initiators, it is preferable that the total of the initiators is in the above-mentioned range.

<<Corrosion inhibitor>> The resin composition in the present invention preferably contains a rust inhibitor. The resin composition contains a rust inhibitor, thereby effectively suppressing the migration of metal ions originating from the metal layer (metal wiring) into the resin composition layer. As the rust inhibitor, the rust inhibitor described in paragraph 0094 of JP 2013-15701 A, the compound described in paragraphs 0073 to 0076 of JP 2009-283711, and JP 2011- The compound described in paragraph 0052 of 59656, the compound described in paragraphs 0114, 0116, and 0118 of JP 2012-194520, etc. Specifically, examples include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridine ring, etc.). Oxazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring) compounds, compounds with thioureas and mercapto groups, Hindered phenolic compounds, salicylic acid derivatives, hydrazine derivatives. Among them, triazole compounds such as triazole and benzotriazole, tetrazole compounds such as tetrazole and benzotetrazole are preferred, 1,2,4-triazole, 1,2,3-benzotriazole , 5-Methyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole are more preferable, and 1H-tetrazole is the best. As commercially available products, KEMITEC BT-C (manufactured by CHEMIPRO KASEI KAISHA, LTD, 1,2,3-benzotriazole), 1HT (manufactured by TOYOBO CO., LTD., 1H-tetrazole), P5T (TOYOBO CO., LTD., 5-phenyl-1H-tetrazole), etc.

When the resin composition contains a rust inhibitor, the content of the rust inhibitor is preferably 0.1-10 parts by mass relative to 100 parts by mass of the resin, and more preferably 0.2-5 parts by mass. There may be only one kind of rust inhibitor, or two or more kinds. When two or more are used, it is preferable that the sum total is the above-mentioned range.

<<Silane Coupling Agent> The resin composition of the present invention may preferably contain a silane coupling agent for improving the adhesion to a common metal material such as electrodes or wiring. Examples of silane coupling agents include the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication WO2011/080992A1, and Japanese Patent Application Publication No. 2014- The compound described in paragraphs 0060 to 0061 of 191252, the compound described in paragraphs 0045 to 0052 of JP 2014-41264, and the compound described in paragraph 0055 of International Publication WO2014/097594. In addition, as described in paragraphs 0050 to 0058 of JP 2011-128358 A, it is also preferable to use two or more different silane coupling agents. In addition, the silane coupling agent used 2-((3-(triethoxysilyl)propyl)aminomethanyl)benzoic acid, triethoxysilylpropylmaleic acid, and the following Compounds are also preferred. In the following formulae, Et represents an ethyl group. As a commercially available product, KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd., N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane) or the like can also be used. [Chemical formula 37]

The silane coupling agent is preferably in the range of 0.1 to 30 parts by mass, and more preferably in the range of 0.5 to 15 parts by mass with respect to 100 parts by mass of the resin. By setting the content of the silane coupling agent to 0.1 parts by mass or more, the adhesion to the metal layer of the film that can be obtained becomes better, and by setting the content of the silane coupling agent to 30 parts by mass or less, it is possible to obtain The heat resistance and mechanical properties of the film become better. There may be only one type of silane coupling agent, or two or more types. When two or more are used, it is preferable that the sum total is the above-mentioned range.

<<Solvent>> In the present invention, when the resin composition is formed into a layered form by coating, it is preferable to blend a solvent with the resin composition. As a solvent, a well-known solvent can be used arbitrarily. For example, compounds such as esters, ethers, ketones, aromatic hydrocarbons, and sulfites can be cited. As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, alkoxy Ethyl ethoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) ), 3-alkoxy propionic acid alkyl esters (for example, 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (for example, 3-methoxy propionic acid methyl ester, 3 -Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (for example, 2-alkoxy Methyl propionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkoxy Ethyl-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. As the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve acetate are preferably mentioned. , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid Ester etc. As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. are preferably mentioned. As aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are preferably mentioned. As the sulfenites, dimethyl sulfenite can preferably be cited.

From the viewpoint of improvement of coating surface properties, etc., a form in which two or more solvents are mixed is also preferable. Among them, it is selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol ethyl A mixed solution composed of two or more of the acid ester, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferred. It is particularly good to use dimethyl sulfoxide and γ-butyrolactone at the same time.

When the resin composition has a solvent, from the viewpoint of coating properties, the content of the solvent is preferably such that the total solid content concentration of the resin composition becomes 5 to 80% by mass, and 5 to 70% by mass is more preferable. Preferably, 10 to 60% by mass is particularly preferred. The solvent content can be adjusted by the desired thickness and coating method. For example, if the coating method is a spin coating method or a slit coating method, the content of the solvent having the solid content concentration in the above-mentioned range is preferable. If it is a spraying method, it is preferable to set it as the amount of 0.1 mass%-50 mass %, and it is more preferable to set it as the amount of 1.0 mass%-25 mass %. By adjusting the amount of the solvent by the coating method, a resin composition layer of a desired thickness can be uniformly formed. There may be only one type of solvent, or two or more types. When there are two or more solvents, it is preferable that the total of them is in the above-mentioned range. Also, from the viewpoint of film strength, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformaldehyde The content of amide relative to the total mass of the resin composition is preferably less than 5% by mass, more preferably less than 1% by mass, more preferably less than 0.5% by mass, and more preferably less than 0.1% by mass.

<<Sensitizing dye>> The resin composition in the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with a thermal base generator, a photobase generator, a thermal radical polymerization initiator, a photopolymerization initiator, etc., to generate electron transfer, energy transfer, heat generation, and the like. Thereby, the thermal base generator, photobase generator, thermal radical polymerization initiator, and photopolymerization initiator undergo chemical changes to decompose, and generate radicals, acids, or bases. For the details of the sensitizing dye, refer to the descriptions in paragraphs 0161 to 0163 of JP 2016-027357 A, and the contents are incorporated into this specification. When the resin composition contains a sensitizing dye, the content of the sensitizing dye relative to the total solid content of the resin composition is preferably 0.01-20% by mass, more preferably 0.1-15% by mass, and more preferably 0.5-10% by mass. Better. The sensitizing dye may be used singly, or two or more of them may be used at the same time.

<<Chain transfer agent>> The resin composition in the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in pages 683-684 of the third edition of the Polymer Dictionary (Edited by The Society of Polymer Science (Japan), 2005). As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These low-activity free radical species can be supplied with hydrogen to generate free radicals, or after oxidation, they can be deprotonated to generate free radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazole Class etc.). When the resin composition contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by mass of the total solid content of the resin composition is preferably 0.01-20 parts by mass, more preferably 1-10 parts by mass, and still more preferably 1 to 5 parts by mass. There may be only one type of chain transfer agent, or two or more types. When there are two or more chain transfer agents, it is preferable that the total of them is in the above-mentioned range.

<<Surfactant>> From the viewpoint of improving coating properties, various surfactants may be added to the resin composition of the present invention. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. In addition, the following surfactants are also preferable. [Chemical formula 38]

When the resin composition contains a surfactant, the content of the surfactant relative to the total solid content of the resin composition is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass. There may be only one type of surfactant, or two or more types. When two or more kinds of surfactants are contained, it is preferable that the total thereof is in the above-mentioned range.

＜＜Higher fatty acid derivatives＞＞ In order to prevent the polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide can be added to the resin composition of the present invention. It is locally present on the surface of the composition during the drying process. When the resin composition has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1-10% by mass relative to the total solid content of the resin composition. There may be only one type of higher fatty acid derivative, or two or more types. When there are two or more higher fatty acid derivatives, it is preferable that the sum total is in the above-mentioned range.

＜＜Other additives＞＞ The resin composition of the invention can be blended with various additives as needed, such as inorganic particles, hardeners, hardening catalysts, fillers, and antioxidants, as long as the effects of the invention are not impaired. , UV absorbers, anti-agglomeration agents, etc. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition.

＜＜＜Restrictions on other contained substances＞＞＞ From the viewpoint of coating surface properties, the moisture content of the resin composition in the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and less than 0.6 The quality% is particularly good.

From the standpoint of insulation, the resin composition of the present invention preferably has a metal content of less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and less than 0.5 mass ppm. Especially good. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are included, the total of these metals is preferably in the above-mentioned range. In addition, as a method of reducing metal impurities inadvertently included in the resin composition, it is possible to select a raw material with a low metal content as the raw material constituting the resin composition, filter the raw material constituting the composition of the present invention, and use The inside of the device is lined with polytetrafluoroethylene, and distillation is carried out under the condition of suppressing pollution as much as possible.

From the viewpoint of wiring corrosion, the resin composition of the present invention preferably has a halogen atom content of less than 500 ppm by mass, more preferably less than 300 ppm by mass, and particularly preferably less than 200 ppm by mass. Among them, less than 5 mass ppm is preferred for those present in the state of halogen ions, less than 1 mass ppm is more preferred, and less than 0.5 mass ppm is particularly preferred. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of the chlorine atom and the bromine atom or the chloride ion and the bromide ion be in the above-mentioned ranges.

<Preparation of resin composition> The resin composition can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and it can be performed by a conventionally known method. In addition, for the purpose of removing foreign substances such as garbage or fine particles in the resin composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be cleaned in advance with an organic solvent. In the filtration process of the filter, multiple filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes and/or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering is performed multiple times, it may be cyclic filtering. In addition, filtration may be performed after pressurization. When filtering is performed after pressurization, the pressure for pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using filters, it can also be used to remove impurities using adsorbents. It can also be combined with filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.

<Electronic component> Next, an embodiment of an electronic component obtained by applying the method of manufacturing a laminate of the present invention will be described. The electronic component 100 shown in FIG. 2 is a so-called three-dimensional mounting device, and a laminated body 101 in which a plurality of semiconductor elements (semiconductor wafers) 101 a to 101 d are laminated is arranged on a wiring board 120. In addition, in this embodiment, the case where the number of stacked layers of the semiconductor element (semiconductor wafer) is 4 layers is mainly described, but the number of stacked layers of the semiconductor element (semiconductor wafer) is not particularly limited. For example, it may be 2 layers, 8 layers, 16 floors, 32 floors, etc. Also, it may be one layer.

Each of the plurality of semiconductor elements 101a to 101d includes a semiconductor wafer such as a silicon substrate. The uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof. The semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) integrally provided on the through electrodes are provided on both surfaces of each semiconductor element.

The laminated body 101 has a structure in which a semiconductor element 101a having no through electrodes and a semiconductor element 101b to 101d having through electrodes 102b to 102d are flip-chip bonded. That is, the electrode pad of the semiconductor element 101a without the through electrode and the connection pad on the semiconductor element 101a side of the adjacent semiconductor element 101b with the through electrode 102b are connected by metal bumps 103a such as solder bumps. And the connection pad on the other side of the semiconductor element 101b having the through electrode 102b and the connection pad on the semiconductor element 101b side of the adjacent semiconductor element 101c having the through electrode 102c are formed by metal bumps 103b such as solder bumps. connect. Similarly, the connection pad on the other side of the semiconductor element 101c with the through electrode 102c and the connection pad on the semiconductor element 101c side of the adjacent semiconductor element 101d with the through electrode 102d are made of metal bumps such as solder bumps. 103c and connected.

An underfill layer 110 is formed in the gaps between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are laminated via the underfill layer 110.

The laminated body 101 is laminated on the wiring board 120. As the wiring substrate 120, for example, a multiple-layer wiring substrate in which an insulating substrate such as a resin substrate, a ceramic substrate, and a glass substrate is used as a base material is used. As the wiring board 120 to which the resin substrate is applied, a plurality of copper-clad laminates (a plurality of printed wiring boards) and the like can be cited.

A surface electrode 120 a is provided on one surface of the wiring substrate 120. The insulating layer 115 in which the rewiring layer 105 is formed is arranged between the wiring substrate 120 and the laminated body 101, and the wiring substrate 120 and the laminated body 101 are electrically connected via the rewiring layer 105. The insulating layer 115 is formed by the manufacturing method of the laminated body of this invention. The insulating layer 115 may have a multiple-layer wiring structure as shown in FIG. 1. One end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the side of the rewiring layer 105 via a metal bump 103d such as a solder bump. In addition, the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump. Furthermore, an underfill layer 110 a is formed between the insulating layer 115 and the laminated body 101. In addition, an underfill layer 110b is formed between the insulating layer 115 and the wiring substrate 120.

<The manufacturing method of an electronic component> Next, the manufacturing method of the electronic component of this invention is demonstrated. The manufacturing method of the electronic component of this invention includes the manufacturing method of the laminated body of the above-mentioned this invention. The manufacturing method of the electronic component of the present invention preferably manufactures a plurality of electronic components under the same preservation process conditions. [Example]

Hereinafter, the present invention will be further specifically explained with examples, and the present invention is not limited to the following examples without departing from the scope of the scope. In addition, as long as there is no particular limitation, "%" and "parts" are quality standards. NMR is the abbreviation for nuclear magnetic resonance.

(Synthesis example 1)

[Polyimide precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and benzyl alcohol (P-1: Polyimide precursor without radical polymerizable group )Synthesis]

14.06g (64.5 millimoles) of pyromellitic dianhydride (dried at 140°C for 12 hours) and 14.22g (131.58 millimoles) of benzyl alcohol were suspended in 50mL of N-methylpyrrolidone, and It is dried by molecular sieve. The suspension was heated at 100°C for 3 hours. The heating was started and a clear solution was obtained after a few minutes. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 mmol) of pyridine and 90 ml of N-methylpyrrolidone were added. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 millimoles) of SOCl _{2 was} added over 10 minutes while maintaining the temperature at -10±4°C. The viscosity increased during the addition of SOCl _2. After diluting with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, 11.08g (58.7 millimoles) of 4,4'-diaminodiphenyl ether was dissolved in 100ml of N-methylpyrrolidone and added dropwise to the reaction mixture at 20~23°C for 20 minutes. The solution obtained. Then, the reaction mixture was stirred at room temperature for one night. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered out, poured into 4 liters of water again, and further stirred for 30 minutes to perform filtration again. Next, the polyimide precursor was dried at 45°C for 3 days under reduced pressure to obtain a polyimide precursor (P-1) containing a repeating unit represented by the following formula.

[Chemical formula 39]

(Synthesis Example 2) [Polyimine precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (P-2: free radical Synthesis of polymerizable polyimide precursor] 14.06g (64.5 millimoles) of pyromellitic dianhydride (dried at 140°C for 12 hours), 18.6g (129 millimoles) of 2-Hydroxyethyl methacrylate, 0.05g of hydroquinone, 10.7g of pyridine and 140g of diethylene glycol dimethyl ether (diethylene glycol dimethyl ether) were mixed and kept at a temperature of 60°C Stirring for 18 hours produced a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, _{after chlorinating the obtained diester with SOCl 2,} it was converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same way as in Synthesis Example 1, and compared with Synthesis Example 1. 1 In the same way, a polyimide precursor (P-2) containing a repeating unit represented by the following formula was obtained. [Chemical formula 40]

(Synthesis Example 3) [Polyimide precursor derived from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (P -3: Synthesis of polyimide precursor with radical polymerizable group] 20.0 g (64.5 millimoles) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 Hour), 18.6g (129 millimoles) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 10.7g of pyridine and 140g of diethylene glycol dimethyl ether, and mix them at 60°C Stirred for 18 hours at a temperature of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate diester. Next, _{after chlorinating the obtained diester with SOCl 2,} it was converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same way as in Synthesis Example 1, and compared with Synthesis Example 1. 1 In the same way, a polyimide precursor (P-3) containing a repeating unit represented by the following formula was obtained. [Chemical formula 41]

(Synthesis example 4) [Synthesis of acrylic polymer (P-6)] 27.0 g (153.2 millimoles) of benzyl methacrylate and 20 g (157.3 millimoles) of N-isopropyl methacrylate Amide, 39 g (309.2 millimoles) of allyl methacrylate, 13 g (151.0 millimoles) of methacrylic acid, polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) 3.55 g (15.4 mmol) and 300 g of 3-methoxy-2-propanol are mixed. In a nitrogen atmosphere, the mixed solution was added dropwise to 300 g of 3-methoxy-2-propanol heated to 75°C over 2 hours. After the dripping was completed, it was further stirred at 75°C for 2 hours under a nitrogen atmosphere. After the reaction, the polymer was poured into 5 liters of water to precipitate the polymer, and the mixture was stirred at a speed of 5000 rpm for 15 minutes. The acrylic resin was removed by filtration, and it was poured into 4 liters of water again, and further stirred for 30 minutes to perform filtration and removal again. Next, under reduced pressure, the obtained acrylic resin was dried at 45° C. for 3 days to obtain an acrylic polymer (P-6) represented by the following formula. [Chemical formula 42]

<Preparation of photosensitive resin composition> The components described below were mixed to prepare a coating liquid of the photosensitive resin composition as a uniform solution. (Composition) Resin: Parts by mass of radical polymerizable compound described in the following table: Parts by mass of the photoradical polymerization initiator described in the following table: Parts by mass of silane coupling agent described in the following table: Parts by mass of the rust inhibitor described in the following table: Parts by mass of the polymerization inhibitor described in the following table: Parts by mass of the base generator described in the following table: Parts by mass of the solvent 1 described in the following table (Dimethyl sulfide): 100 parts by mass Solvent 2 (γ-butyrolactone): 25 parts by mass

[Table 6]

The abbreviations listed in the table are as follows. (Resin) P-1 to P-3: Polyimide precursors (P-1) to (P-3) synthesized in Synthesis Examples 1 to 3 P-5: Matrimid 5218 (manufactured by Huntsman Corporation, closed ring type) Polyimide) P-6: Acrylic polymer synthesized in Synthesis Example 5 (P-6) (acrylic resin) P-7: Polymethylmethacrylate (Mw=15000, Sigma-Aldrich Co . LLC.)

(Radical polymerizable compound) B-1: SR209 (manufactured by Sartomer company Inc., tetraethylene glycol diacrylate) B-2: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co, Ltd., ethoxy B-3: A-TMMT (manufactured by Shin-Nakamura Chemical Co, Ltd., pentaerythritol tetraacrylate) B-4: A-DPH (manufactured by Shin-Nakamura Chemical Co, Ltd., Dipentaerythritol hexaacrylate)

(Photo-radical polymerization initiator) C-1: IRGACURE OXE 01 (manufactured by BASF, oxime compound) C-2: IRGACURE OXE 02 (manufactured by BASF, oxime compound) C-3: IRGACURE-784 (manufactured by BASF, Metallocene compound) C-4: ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION, oxime compound)

(Silane coupling agent) D-1: KBM-602 (Shin-Etsu Chemical Co., Ltd., a silane compound with an amine group) D-2: 2-((3-(triethoxysilyl group) Propyl) aminomethanyl) benzoic acid (manufactured by Aquila Pharmatech LLC, a carboxyl-containing silane compound) D-3: Triethoxysilylpropyl maleic acid (manufactured by Gelest, Inc., a carboxyl compound) Silane compound)

(Anti-rust agent) E-1: KEMITEC BT-C (manufactured by CHEMIPRO KASEI KAISHA, LTD, 1,2,3-benzotriazole) E-2: 1HT (manufactured by TOYOBO CO., LTD., 1H-tetrazole) ) E-3: P5T (manufactured by TOYOBO CO., LTD., 5-phenyl-1H-tetrazole)

(Polymerization inhibitor) F-1: 4-methoxyphenol F-2: p-benzoquinone F-3: 1-nitroso-2-naphthol

(Alkali generator) A-1, A-21, A-40: Compounds of the following structure (thermal base generator) A-43: WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd., photo base generator). In addition, this compound is also a compound that decomposes even if heated to generate a base. That is, it is also a thermal base generator.) [Chemical formula 43]

<Manufacturing of laminated body> After pressure filtering each photosensitive resin composition through a filter with a pore width of 0.8 μm, it is applied in a layered form by spin coating on a silicon wafer and used The hot plate was dried at 100°C for 5 minutes to form a photosensitive resin composition layer. Next, after performing the preservation process (PCD process) at the time and temperature described in the following table, the photosensitive resin composition layer was exposed ^{using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ/cm 2} . Next, the photosensitive resin composition layer after exposure was subjected to a preservation process (PED process) at the time and temperature described in the following table, and then developed using cyclopentanone for 60 seconds to form a hole with a diameter of 10 μm. Next, after performing a storage process (PDD process) at the time and temperature described in the following table, it was heated at 230° C. for 3 hours in a nitrogen environment to form a resin layer (pattern). Next, the heated resin layer (pattern) is cooled to room temperature, and the storage process (PBD process) is performed at the time and temperature described in the following table, followed by a copper plating process to form copper with a thickness of 5 μm on the resin layer Thin film, thereby forming a laminate 1. In addition, place it in a clean thermo-hygrostat (manufactured by (ESPEC CORP.), PCR-3J) adjusted to the set temperature described in the following table to perform each preservation process. Next, after irradiating the copper thin film of the laminate 1 with oxygen plasma, the application of the photosensitive resin composition, exposure, development, heating, and various storage processes are performed again, and then copper plating is performed to form a copper thin film with a thickness of 5 μm on the resin layer. And laminated body 2 was obtained. Next, after irradiating the copper thin film of the laminate 2 with oxygen plasma, the application of the photosensitive resin composition, exposure, development, heating, and various storage processes are performed again, followed by a copper plating process to form copper with a thickness of 5 μm on the resin layer. The layered product 3 was obtained by forming a thin film.

[Table 7]

The storage time in each condition described in the above table is the elapsed time after the surface temperature reaches the set temperature. The fluctuation range of the surface temperature in each storage process is 5°C or less. In addition, the average surface temperature in each storage process is approximately the same as the set temperature.

<Evaluation> [Peeling Defect (Evaluation 1)] The laminate 2 was cut in the vertical direction and a cross section with a width of 5 mm was observed to confirm whether there was peeling between the resin layer/resin layer and between the copper/resin layer. If no peeling occurs. It means that it has excellent adhesion and becomes a better result.

A: No peeling

B: 1~2 peeling occurred

C: 3~5 peeling occurred

D: More than 6 peels occurred

[Peeling defect (evaluation 2)]

The laminated body 3 was cut in the vertical direction and a cross section of 5 mm in width was observed to confirm whether there was peeling between the resin layer/resin layer and the copper/resin layer. If no peeling occurs. It means that it has excellent adhesion and becomes a better result.

A: No peeling

B: 1~2 peeling occurred

C: 3~5 peeling occurred

D: More than 6 peels occurred

[Boundary resolution (evaluation 3)]

A stepper (Nikon NSR2005 i9C) was used to expose the photosensitive resin composition layer on the silicon wafer. The exposure was performed with i-rays, and exposure was performed at a wavelength of 365 nm, with ^{an exposure energy of 200 mJ/cm 2} up to 5 μm to 25 μm, using a light shield of a fuse box in increments of 1 μm. The exposed photosensitive resin composition layer was developed using cyclopentanone and propylene glycol methyl ether acetate as a developing solution. Specifically, cyclopentanone was sprayed on the exposed photosensitive resin composition layer, and then propylene glycol methyl ether acetate was sprayed to perform development for 60 seconds. The line width of the silicon wafer exposed at the bottom of the fuse box was evaluated based on the following criteria. The smaller the line width, the more it means that the width of the metal wiring formed in the subsequent electroplating process can be made finer, and it becomes a better result. The measurement limit is 5μm. The results are shown in the table.

A: 5μm or more and 8μm or less B: more than 8μm and 10μm or less C: more than 10μm and 15μm or less D: more than 15μm

[Table 8]

As shown in the above table, in the example in which the preservation process was performed, it was possible to produce a laminate with excellent adhesiveness. In addition, the photosensitive resin composition of the composition 1-12 using the polyimide precursor as the resin has high boundary resolution, and the photosensitive resin composition of Examples 1 to 33, 36, and 37 using the photosensitive resin composition The laminate can further reduce the width of the metal wiring.

100‧‧‧Electronic component 101a～101d‧‧‧Semiconductor component 101‧‧‧Laminated body 102b～102d‧‧‧Through electrode 103a～103e‧‧‧Metal bump 105‧‧‧Rewiring layer 110, 110a, 110b‧ ‧‧Underfill layer 115‧‧‧Insulation layer 120‧‧‧Wiring board 120a‧‧‧Surface electrode 201～204‧‧‧Resin layer 301～303‧‧‧Metal layer 401～403‧‧‧Trench 500‧‧‧ Layered body

Fig. 1 is a schematic diagram showing the structure of an embodiment of a laminate. Fig. 2 is a schematic diagram showing the structure of an embodiment of an electronic component.

Claims (14)

A method for manufacturing a laminate, comprising: a process for forming a photosensitive resin composition layer, and applying a silane coupling agent selected from a polyimide precursor, a polyimide, and a polybenzoxazole precursor on the support And the photosensitive resin composition of the resin in the polybenzoxazole and the photopolymerization initiator to form a photosensitive resin composition layer. The resin in the photosensitive resin composition is a polyimide precursor, and the polyimide The imine precursor contains a radical polymerizable group, or the photosensitive resin composition contains a radical polymerizable compound other than the polyimide precursor; the exposure process involves exposing the photosensitive resin composition layer into a pattern The developing process, the photosensitive resin composition layer is developed to form a pattern; the heating process, the aforementioned pattern is heated; and the metal layer forming process, the metal layer is formed on the heated pattern; and the photosensitive resin composition The preservation process is performed between the object layer formation process and the aforementioned exposure process, at least one of between the aforementioned exposure process and the aforementioned development process, between the aforementioned development process and the aforementioned heating process, and between the aforementioned heating process and the aforementioned metal layer forming process During the storage process, in the aforementioned storage process, after the surface temperature reaches a certain temperature, it is stored in this state for more than 5 minutes. The method for manufacturing a laminate as described in the first item of the patent application, wherein the storage process is performed between the exposure process and the development process. The method for manufacturing a laminate as described in the second item of the scope of patent application, wherein the storage process performed between the exposure process and the development process satisfies the following formula:

T1 is the average surface temperature in the storage process performed between the exposure process and the development process and the unit is K, t1 is the time of the storage process performed between the exposure process and the development process and the unit is minutes . The method for manufacturing a laminated body as described in claim 1, wherein the preservation process performed between the photosensitive resin composition layer forming process and the exposure process satisfies the following formula:

T2 is the average surface temperature in the storage process performed between the photosensitive resin composition layer forming process and the exposure process, and the unit is K, t2 is the difference between the photosensitive resin composition layer forming process and the exposure process The time for the aforementioned storage process to be performed in minutes and the unit is minutes. The method for manufacturing a laminate as described in item 1 or item 2 of the scope of patent application, wherein the storage process is performed between the development process and the heating process. The method for manufacturing a laminate as described in item 5 of the scope of patent application, wherein the storage process performed between the development process and the heating process satisfies the following formula:

T3 is the average surface temperature in the storage process performed between the development process and the heating process and the unit is K, t3 is the time of the storage process performed between the development process and the heating process and the unit is minutes . The method for manufacturing a laminate as described in item 1 or item 2 of the scope of patent application, wherein the storage process is performed between the heating process and the metal layer forming process. The method of manufacturing a laminate as described in item 1 or item 2 of the scope of the patent application, wherein the polyimide precursor includes a repeating unit represented by the following formula (1),

In formula (1), A ²¹ and A ²² each independently represent an oxygen atom or -NH-, R ²¹ represents a divalent organic group, R ²² represents a tetravalent organic group, and R ²³ and R ²⁴ each independently represent a hydrogen atom or Monovalent organic group. The method for manufacturing a laminate as described in claim 8, wherein in the aforementioned formula (1), ^{at least one of R 23} and R ²⁴ contains a radical polymerizable group. The method for manufacturing a laminate as described in item 8 of the scope of patent application, wherein R ²² in the aforementioned formula (1) is a tetravalent group containing an aromatic ring. The method for manufacturing a laminate as described in item 1 or item 2 of the scope of the patent application, wherein the following series of cycles are carried out for more than 2 cycles, that is, the pattern after the metal layer formation process is sequentially subjected to the aforementioned photosensitive The photosensitive resin composition layer formation process, the exposure process, the development process, the heating process, and the metal layer formation process, and between the photosensitive resin composition layer formation process and the exposure process, the exposure process and the development process Between processes, between the aforementioned development process and the aforementioned heating process, and between the aforementioned heating process and the aforementioned metal layer shape In at least one of the production processes, the aforementioned preservation process is performed. The manufacturing method of the laminated body described in the 1st or 2nd item of the scope of patent application is a manufacturing method of the laminated body of a multiple-layer wiring structure. A method for manufacturing an electronic component, comprising: a process of forming a photosensitive resin composition layer, and applying a silane coupling agent, selected from polyimide precursors, polyimines, and polybenzoxazole precursors, on a support And the photosensitive resin composition of the resin in the polybenzoxazole and the photopolymerization initiator to form a photosensitive resin composition layer. The resin in the photosensitive resin composition is a polyimide precursor, and the polyimide The imine precursor contains a radical polymerizable group, or the photosensitive resin composition contains a radical polymerizable compound other than the polyimide precursor; the exposure process involves exposing the photosensitive resin composition layer into a pattern The development process, which develops the aforementioned photosensitive resin composition layer to form a pattern; the heating process, which heats the aforementioned pattern; and the metal layer formation process, which forms a metal layer on the heated pattern; and the aforementioned photosensitive resin composition The preservation process is performed between the object layer formation process and the aforementioned exposure process, at least one of between the aforementioned exposure process and the aforementioned development process, between the aforementioned development process and the aforementioned heating process, and between the aforementioned heating process and the aforementioned metal layer forming process During the storage process, in the aforementioned storage process, after the surface temperature reaches a certain temperature, it is stored in this state for more than 5 minutes. The method for manufacturing electronic components as described in item 13 of the scope of the patent application, wherein a plurality of electronic components are manufactured under the same conditions of the aforementioned preservation process.

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